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The Potential Applications of Graphene (and Related Compounds) Relevant to the NDA’s Decommissioning Mission P Davies1, S Walton1, S Ashley1, A Tzalenchuk2, C Williams3 and P Wiper3 1 NSG Environmental Ltd.
2 National Physical Laboratory
3 University of Manchester
Direct Research Portfolio Purchase Order: NDA015384 Date: March 2017 Contractor Ref: NS4145-500-005 Issue: 3
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Preface This report has been prepared by NSG Environmental under contract to the Nuclear Decommissioning Authority (NDA). The views expressed and conclusions drawn are those of the authors and do not necessarily represent those of NDA. Conditions of publication This report is made available under NDA’s Transparency Policy. In line with this policy, NDA is seeking to make information on its activities readily available, and to enable interested parties to have access to and influence on its future programmes. The report may be freely used for non-commercial purposes. However, all commercial uses, including copying and re-publication, require NDA’s permission. All copyright, database rights and other intellectual property rights reside with NDA. Applications for permission to use the report commercially should be made to the NDA’s Communications department at the address below. Although great care has been taken to ensure the accuracy and completeness of the information contained in this publication, NDA cannot assume any responsibility for consequences that may arise from its use by other parties. © Nuclear Decommissioning Authority 2017. All rights reserved Communications Department NDA Herdus House Westlakes Science and Technology Park Moor Row Cumbria CA24 3HU
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Glossary
AGH Amidoxime GO Hydrogel
CNT Carbon Nanotube CPI Centre for Process Innovation
CVD Chemical Vapour Deposition DOE US Department of Energy
DRP Direct Research Portfolio EARP Enhanced Actinide Removal Plant
GBM Graphene-Based Material
GFET Graphene Field Effect Transistors GLEEP Graphite Low Energy Experimental Pile
GO Graphene Oxide HAL High Active Liquors
IEC International Electrotechnical Commission ISO International Organization of Standardization
LP&S Legacy Ponds and Silos
NDA Nuclear Decommissioning Authority NPL National Physical Laboratory
NSF US National Science Foundation ONR Office for Nuclear Regulation
OSTI Office of Scientific and Technical Information PNNL Pacific Northwest National Laboratory
POCO Post Operation Clean Out
R&D Research and Development REACH Registration, Evaluation, Authorisation & restriction of CHemicals
ROV Remotely Operated Vehicle SETP Segregated Effluent Treatment Plant
SiC Silicon Carbide SIXEP Site Ion Exchange Plant
STP Solvent Treatment Plant
UoM University of Manchester
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Contents
1 Introduction ......................................................................................................................... 4
1.1 Document Scope ....................................................................................................... 5
2 The Properties of Graphene of Relevance to the Nuclear Decommissioning Industry...... 5
2.1 Water Decontamination ............................................................................................. 6
2.1.1 Nano-Filtration ....................................................................................................... 6
2.1.2 Adsorption .............................................................................................................. 7
2.2 Isotopic Separations .................................................................................................. 8
2.3 Composite Materials for Waste Immobilisation and Disposal ................................... 9
2.3.1 Cement Composites .............................................................................................. 9
2.3.2 Polymer Composites ............................................................................................ 10
2.4 Sensors for Radiation/Molecular Adsorption ........................................................... 11
2.4.1 Radiation Detection ............................................................................................. 11
2.4.2 Molecular Detection ............................................................................................. 11
2.5 Properties Relevant to Nuclear Applications ........................................................... 12
2.6 Summary ................................................................................................................. 14
3 Graphene Research and Development Areas ................................................................. 14
3.1 Methodology ............................................................................................................ 15
3.2 Summary ................................................................................................................. 16
4 Correlation Between the Identified Graphene Research Areas and NDA Decommissioning Research and Development Needs ........................................................... 17
4.1 Methodology ............................................................................................................ 17
4.2 NDA Decommissioning Research and Development Needs .................................. 18
4.3 Identification of Correlations .................................................................................... 18
4.3.1 Spent Fuels .......................................................................................................... 25
4.3.2 Nuclear Materials ................................................................................................. 27
4.3.3 Integrated Waste Management ........................................................................... 27
4.3.4 Site Decommissioning and Remediation ............................................................. 28
4.4 Identification of Research Gaps and Opportunities ................................................. 30
4.4.1 Potential Research Gaps ..................................................................................... 30
4.4.2 Potential Opportunities ........................................................................................ 31
5 The Potential Limitations of the Use of Graphene in Nuclear Decommissioning Applications ............................................................................................................................. 32
5.1 Cost.......................................................................................................................... 32
5.2 Manufacturing Scale Up .......................................................................................... 34
5.3 Environmental Safety Impacts ................................................................................. 35
5.4 Regulatory Concerns ............................................................................................... 36
5.5 Lack of Standardisation ........................................................................................... 36
5.6 Radiation Tolerance................................................................................................. 37
6 Conclusions ...................................................................................................................... 38
6.1 Key Synergies Identified .......................................................................................... 39
7 Recommendations ........................................................................................................... 39
8 References ....................................................................................................................... 41
Appendix A .............................................................................................................................. 45
Detailed Output from the Desktop Review of Graphene research areas ......................... 45
Appendix B .............................................................................................................................. 88
The NDA Estate’s Research and Development Needs ....................................................... 88
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1 Introduction Research and development (R&D) is fundamental to ensuring the cost-effective delivery of the Nuclear Decommissioning Authority (NDA) mission. Together with innovation and the sharing of national and international good practice, the intelligent application of R&D can reduce decommissioning costs and timescales, reduce environmental impact and improve safety. Through the Direct Research Portfolio (DRP), the NDA supports early technical innovation to address identified needs, risks or opportunities across the NDA estate [1]. These multi-site needs, risks and opportunities are identified through engagement between the NDA and the nuclear estate, and summarised in the NDA Technical Baseline document [2]. The NDA has recently identified graphene technology as a potentially promising area that could offer some benefits to the NDA mission. The NDA is aware of some of the novel properties of graphene and its compounds that could enable the use of these new materials in a wide range of applications. There is a broad range of research being undertaken by several research groups in the UK, e.g. University of Manchester (UoM), the National Physical Laboratory (NPL) and the University of Cambridge, as well as abroad which is developing a deeper understanding of the chemical and physical properties of graphene and its compounds, potential applications and manufacturing technologies. There are also some significant collaborative research programmes e.g. the EU funded Graphene Flagship which aims to take graphene from research laboratories into society by 2023. The EU Graphene Flagship has a budget of €1 billion and represents a joint, coordinated research approach on an unprecedented scale, forming Europe's biggest ever research initiative. The Graphene Flagship is tasked with bringing together academic and industrial researchers, to take graphene from the realm of academic laboratories into European society. The growing consortium now consists of over 150 academic and industrial research groups in 23 countries, with NPL and the UoM’s National Graphene Institute participating and playing prominent roles in the project from its inception. Furthermore, the Flagship now includes associate-member institutions from outside Europe. Innovate UK is a governmental funding body who work with people, companies and partner organisations to find and drive the science and technology innovations that will grow the UK economy. Within this remit, Innovate UK has been involved in the funding of graphene based research and represents a source of information for graphene research information. In 2014, The Centre for Process Innovation (CPI) was setup as the home of a £14 million Graphene Applications Innovation Centre, to provide facilities and expertise to help companies to develop, prove, prototype and scale up graphene based products and processes. Rapid progress Catapults such as the CPI are helping UK businesses accelerate the commercialisation of new and innovative technologies and provides another focal point for information on graphene based research development. The Clarivate Analytics’ Web of Science database [3] currently lists 90,414 research articles on various topics related to graphene. The extent of interest and research in this material has meant that keeping abreast of developments in this area and
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potential applications has been challenging, such that the knowledge of graphene technology and relevant applications is not very well known across the NDA estate. Therefore the NDA would like to raise awareness across its estate about the properties and potential opportunities for the use of graphene and its compounds in nuclear decommissioning. This will enable organisations engaged in decommissioning to better assess potential applications and allow better communication with the research community. This in turn could facilitate the identification and funding of further specific R&D in key areas. 1.1 Document Scope This document follows on from the “Summary of Graphene (and Related Compounds) Chemical and Physical Properties” report [4], which was intended to be used as a reference point for the NDA and the NDA estate for graphene related information. This document reviews existing graphene research, both within academia and industry, and attempts to identify correlations between current graphene research and the NDA R&D requirements. Furthermore, any potential limitations in the use of graphene have also been highlighted. This document includes the following sections:
• The properties of graphene relevant to the nuclear decommissioning industry; • Graphene research areas; • Correlations between the identified graphene research areas and NDA
decommissioning research and development needs; • The limitations of the use of graphene in nuclear decommissioning
applications; • Conclusions.
The term “graphene”, as used in this document, has been used to describe a collection of graphene-based materials (GBMs) including, but not limited to, single-layer graphene, graphene nanoplatelets, graphene oxide (GO), reduced graphene oxide and functionalized/chemically modified graphene.
2 The Properties of Graphene of Relevance to the Nuclear Decommissioning Industry
The properties of graphene of relevance to the nuclear decommissioning and remediation are outlined in this section and directly follows on from the information presented in Reference [4]. Although the application of graphene in the nuclear decommissioning industry is still in its infancy, there have already been a number of early research projects and associated publications in this area. The Unity2 team comprising NSG, UoM and the NPL have reviewed the literature and identified a series of publications directly relevant to nuclear decommissioning and remediation that have demonstrated the use of graphene. These publications and key research areas are summarised below, and include:
• Water decontamination;
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• Isotopic separation; • Composite materials; • Sensors.
The properties of graphene that make it attractive to nuclear applications have also been identified. 2.1 Water Decontamination Aqueous effluents arise from a range of operational and decommissioning activities. The effluents can contain a complex mix of radioactive and non-radioactive species. Effluents are treated in dedicated plants, such as Sellafield’s Site Ion Exchange Plant (SIXEP), Enhanced Actinide Removal Plant (EARP) and Solvent Treatment Plant (STP), to remove radionuclides in order to satisfy strict regulatory limits on, and progressively reduce radioactive discharges into the environment. Current treatment strategies rely on a mix of evaporation, precipitation, ion-exchange and filtration processes. In some cases these approaches suffer from poor selectivity in the presence of competing species and in the future the composition of the effluent stream is likely to change as operations cease. Improving the materials and processes used in effluent treatment may simultaneously reduce operating costs, help to comply with discharge regulations and reduce the total volume of waste for future disposal. In some instances, radionuclides have already escaped into environmental water sources (e.g. due to past effluent discharges from Sellafield, the accidents at the Fukushima Daiichi power plant and the leaking waste tanks at the Hanford Site). Contaminated sites must be treated to prevent a direct radiation risk to the public and the environment as well as avoiding the undermining of confidence in future nuclear energy production. Environmental decontamination is still a costly and challenging process and although some approaches to decontamination have been demonstrated to be effective in the laboratory, they perform less well in the presence of competing ions and in realistic environmental conditions. A recurring problem in both aqueous effluent treatment and environmental decontamination is poor selectivity and better, highly selective materials are required. GO is particularly appealing for these applications because it can be fabricated into a membrane material with relative ease and subsequently used for nano-filtration, or alternatively dispersed in water and used as an adsorbent for radionuclides. In addition, it is non-toxic and biodegradable so it is safe to introduce into the aqueous environment. Two specific research areas relating to GO in water decontamination are discussed below. 2.1.1 Nano-Filtration GO membranes can be fabricated by vacuum filtration of an aqueous suspension of GO sheets. The resulting film has a layered structure of graphene sheets comprising oxygen-containing groups. The material swells when immersed in water, forming an array of uniform 2D nano-channels in between individual sheets. The extremely high water flux observed through the membrane [5] has opened up the possibility of GO being used in water purification applications for nano-filtration.
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In the last few years, impressive progress has been made in the development of GO membranes as highly selective ionic/molecular filters [6]. The factor determining whether a given solute will pass through the membrane is its size, with only small solutes able to enter the GO channels and pass through the membrane. Although the experiments conducted to date did not focus on radioactive contaminants, many of those that were investigated can be considered as radioactive analogues. Recently, computer modelling has predicted that GO membranes could be used for the separation of the long-lived and extremely problematic isotope, Tc99, from competing species, such as sulphate and chloride ions, in contaminated water [7]. Instead of taking advantage of the nano-channels created by GO when suspended in water, an alternative approach could be to create size specific pores within the graphene or GO surface using an ion beam when suspended on a surface to generate a graphene/GO ‘sieve’. The resulting material could be used to filter solutes of defined size. This emerging research field is highly appealing for the diverse nature of effluent treatment and decontamination separation problems faced by the nuclear decommissioning industry. A nano-filtration process is amenable to miniaturisation and incorporation into a portable form that could be used for localised effluent treatment. 2.1.2 Adsorption Many approaches used to remove radionuclides from the environment rely on adsorbents due to their simplicity and application at a large scale. Commonly used materials for aqueous radionuclides include clay minerals, metal oxides, biomaterials and activated carbons. However, in many cases these materials exhibit poor adsorption capacities, low efficiencies and often they do not work across a broad range of environmental conditions, such as at low pH. Due to their high surface area and abundance of oxygen-containing groups, GO flakes can be used as adsorbents instead. Romanchuk et al. demonstrated that GO was an extremely effective adsorbent for many of the most toxic and radioactive long-lived radionuclides from contaminated water [8]. They observed effective adsorption of cationic contaminant radionuclides including the actinides (Am, Th, Pu, Np, U) and long-lived, high yield fission products (Sr, Eu) from a simulated nuclear effluent that contained both competing ions, such as sodium and calcium, and complexing agents, including acetate and citrate. However, poor adsorption was observed for the mainly anionic Tc species, due to the negative charge of GO in normal conditions. Many other research groups have reported GO as effective adsorbents for U [9, 10], Am and Pu [11], Eu and Cs [12], Sr [13] and Th [14]. GO typically displays rapid adsorption and much higher maximum adsorption capacities compared to traditional adsorbents, especially for the actinides. Experimental techniques (up to 300 mg per gram of GO), supported by density functional theory calculations, have shown that the radionuclides predominantly bind to the epoxy and hydroxyl sites. The 2D structure of GO maximizes the accessibility of the oxygen groups, contributing to the very high adsorption capacity. The uses of GO as an adsorbent for aqueous radionuclides has also been reviewed [15]. Although GO is relatively expensive compared to clay minerals and other carbon-
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based materials such as activated carbons, GOs may be synthesised at low price in the near future (see Section 5.2) and its high adsorption capacity means that comparatively less adsorbent is needed. Alternatively, the oxygen-containing sites in GO can be functionalised by chemical grafting to enhance selectivity and adsorption capacity. These enhancements are due to a synergistic effect of the high chemical specificity of the functional groups combined with the high surface area and high density of oxygen groups in GO. Examples of GO functionalities that display enhanced radionuclide adsorption include Bayberry tannins for Sr [16], polyaniline for U, Eu, Sr, Cs [17], polydopamine for U [18] and an amidoxime GO hydrogel (AGH) for U [19]. In particular, AGH was found to have a high efficiency for U adsorption and a capacity of 400 mg/g, much higher even than those capacities observed in normal GO. In addition, this adsorbent material was able to remove U from simulated seawater, containing competing species, with U present only at ppb or ppm concentrations, ranking it amongst the most effective U adsorbents ever reported. In the work of Romanchuk et al., GO dispersions readily coagulated following adsorption of radionuclides, facilitated by the adsorbed ions cross-linking between individual sheets. The resulting agglomeration could easily be filtered. It is easy to see how the combined adsorption and coagulation properties of GO could be followed by ultrafiltration of the resulting particles. Combined with the simplicity of industrial scale up of GO production, these properties make GO a promising new material for radionuclide separation and removal. 2.2 Isotopic Separations Another separation application involves the use of monolayer graphene (created by Chemical Vapour Deposition (CVD)) to separate hydrogen and deuteron ions. This pioneering work by researchers at the UoM demonstrated a scalable and competitive way for hydrogen isotope enrichment and may also be of use for the removal of tritium from waste streams. Using electrical measurements and mass spectrometry, it was found that deuterons permeate through graphene much slower than hydrogen ions, resulting in a separation factor of ≈10 at room temperature. The hydrogen ion conductivity of graphene was comparable to commercially available Nafion films, potentially offering a competitive and scalable way for hydrogen isotope enrichment. Moreover, the scale-up potential of graphene using techniques such as CVD provides a realistic prospect of graphene being implemented in industry for hydrogen isotope separation [20]. Zhang et al. have performed quantum calculations to compute activation energies for isotopic hydrogen ion permeation through graphene. They demonstrated that the ratios between different isotopes were in close agreement with the experimental permeation velocity ratios [21]. Researchers at Pacific Northwest National Laboratory (PNNL) were also able to remove low concentrations of radioactive tritiated water from large volumes of contaminated aqueous effluent using GO membranes [22]. Three different membrane thicknesses were investigated, with enhanced separation potentially achievable using thicker membranes, at the expense of lower permeation rates. PNNL researchers observed a slightly different mechanism of separation, whereby normal, deuterated and tritiated water was transported through the oxygenated
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regions of the membrane at different rates, via a proton-hopping mechanism, and not transport through the membrane by simple diffusion. The two isotopic approaches outlined above for separating hydrogen ions and tritiated water utilised graphene and GO respectively. The properties of these two materials are very different, with the graphene required for hydrogen isotope separations having minimal defects, whilst the separation of tritiated water requiring GO that has lots of defects in the form of oxygenated groups, which are required to facilitate the transport of water through the membrane. 2.3 Composite Materials for Waste Immobilisation and Disposal 2.3.1 Cement Composites The ability to safely dispose of radioactivity and mitigate its migration into the environment over geological timescales is critical in underpinning nuclear waste management strategies. Typically, mobile radionuclides must be immobilised before potential transportation and final disposal in a long-term storage facility. For low and intermediate level waste this conventionally involves their immobilisation in Portland cement based grouts. However, Portland cement is brittle and has a weak tensile strength because of relatively large pores that may initiate microcracks. A portion of the cement can be replaced by some supplementary materials that may act to improve the mechanical properties, by delaying the development of microcracks and therefore improve the tensile strength of the cement. There are examples of researchers using low-dimensional nanomaterials, such as carbon nanotubes (CNTs) [23], to enhance the mechanical properties of cement. The nanomaterials are able to fill cracks that develop in the cement during setting, bridging between the interfaces on either side of the crack. Materials with low aspect ratios (length to width ratios), excellent intrinsic strength and toughness are suitable. GO is particularly suitable as an additive because of its excellent mechanical properties, ease of dispersibility in water and abundance of reactive oxygen-containing groups that can bond within the cement matrix. Gong et al. [24] made a GO-cement composite via a high shear mixture to improve the distribution of GO in the cement matrix with 0.03 wt.% of GO. They investigated the resulting change in porosity and influence on compressive tensile strength compared to the pure Portland cement. They observed that the composite exhibited 13.5% lower porosity, 27.7% fewer capillary pores and a 40% increase in 28-day compressive and tensile strength. The refinement in pore structure was attributed to an enhancement in the degree of hydration. Pan et al. [25] added 0.05 wt.% of GO and observed a 33% improvement in the compressive strength and observed the ability of GO to fill cracks in the cement. Sedeghat et al. [26] investigated the thermal diffusivity and electrical conductivity of a GO-cement composite and concluded that both increased relative to the pure cement. High thermal diffusivity is important to dissipate the heat generated by the hydration process. The main disadvantage to adding GO to cement is that the workability is significantly reduced. Additives (e.g. zeolites or bentonite) can be used to reduce the mobility of radionuclides through the pores of cement based wasteforms. Since the adsorptive properties of GO have also been proven (Section 2.1.2), the addition of GO has the
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potential to simultaneously improve the mechanical, thermal and radionuclide mobility properties of the cement. Although the work outlined above [23, 24, 25, 26] was specific to the civil engineering and building materials, the potential to enhance cement properties through the addition of GO may be useful for nuclear waste conditioning. The improvement in the cement’s mechanical strength, enhanced thermal diffusivity and potentially improved radionuclide retention properties would all be beneficial for radioactive waste conditioning. The impact of reduced porosity (described in Reference [24]) on nuclear waste conditioning is not known and further research would be required to fully understand the short and long term impact of cement/GO composites on waste conditioning. The defects found within GO membranes (i.e. the abundance of oxygen containing groups) make this material a good additive due to its ability to form chemical bonds with the matrix material. Graphene with few or minimal defects is unlikely to be as successful owing to its inert nature. 2.3.2 Polymer Composites The conditioning of some radioactive waste types are incompatible with Portland cement. For example, aluminium, uranium and Magnox corrode in the alkaline cement matrix, with the corrosion products expanding and damaging the wasteform. High molecular weight polymeric encapsulants have been proposed as an alternative approach for these problematic waste types. The advantage of these materials is that they are generally stronger than cement with improved performance for leaching of radionuclides into the matrix. They are also resistant to acids, alkalis and organic solvents. A vinyl ester styrene is already in use at a waste treatment plant in Trawsfynydd in Wales to encapsulate ion-exchange resins, and other polymer-based waste forms are being considered. Graphite Low Energy Experimental Pile (GLEEP) fuel at Harwell has also been conditioned using polymers (epoxy resin) to isolate the waste and infill residual voidage [27]. However, polymers with additives display lower heat capacity and thermal conductivity compared to cements, leading to possible problems for large-scale polymer encapsulation, in the context of heat generation due to radioactive decay. Rafiee et al. synthesized an epoxy-graphene nanocomposite and showed that the graphene flakes could be homogeneously dispersed [28]. With only 0.1 wt.% graphene flakes they demonstrated 31% greater Young’s modulus (stress to strain ratio), 40% increase in tensile strength and 53% increase in fracture toughness than pristine epoxy. The improvements in mechanical properties were found to be similar to those with CNTs, but achieved with much lower weight fractions. The improved properties relative to CNTs are thought to be due to enhanced adhesion between the graphene and polymer matrix, high surface area and 2D geometry of graphene. Graphene-polymer nanocomposites have also demonstrated improved thermal properties with a shift in the glass transition temperature of 30°C [29]. Another group have demonstrated up to 70% and 57% increases in tensile strength and Young’s modulus, respectively, upon addition of just 0.9 wt.% graphene [30]. Those researchers also observed that smaller graphene flakes improved dispersion in the polymer melt and reduced the likelihood of introducing free volume into the matrix. A useful review on the mechanical properties of epoxy/nanomaterial (graphene,
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graphene oxide and carbon nanotubes) has recently been published by NPL and Kingston University London [31]. 2.4 Sensors for Radiation/Molecular Adsorption Graphene has excellent electronic properties (e.g. electrical conductivity) making it an attractive material for use in sensors. However, the 2D nature of graphene means that it is unable to absorb radiation, such that the structure has relatively poor radiation resistance despite its aromatic nature, being damaged by alpha, beta and gamma radiation [1]. Despite this perceived weakness, graphene and related compounds have been successfully incorporated into sensors and detectors by coupling the graphene to an absorber material. Specific examples are presented in Sections 2.4.1 and 2.4.2 below and relate to the use of graphene in radiation and molecular detection. 2.4.1 Radiation Detection There is a need for inexpensive, low-power, size-scalable detection devices, which are exceptionally sensitive to X-rays, gamma-rays, and neutrons. Such high performance sensors could be used for detecting the presence of nuclear material and radionuclides. One major challenge in the development of sensors for the detection of ionising radiation is achieving high-energy resolution at room temperature. Due to its exceptional electronic properties (high charge carrier mobility, low noise and extreme sensitivity to changes in local electric fields) the use of graphene in sensor devices could help address these challenges. Several groups have demonstrated the use of graphene field effect transistors (GFETs), for the detection of radiation [32, 33]. In these devices, graphene is mounted upon a radiation-absorbing semiconductor (such as SiC, CdTe and CaAs), separated by a thin buffer layer. When the radiation interacts with the underlying absorber material it deposits energy and perturbs the local electric field of the material. The detection mechanism relies heavily on the high sensitivity of graphene to detecting changes in the electric field due to this radiation-induced event. This can be interpreted from the measured current or resistance upon application of a gate voltage across the GFET. The decoupling of the absorber and detector in this manner also offers additional benefits via the flexibility in the choice of the absorber material. The detectors showed low noise, low power detection of radiation and operation at room temperature. Zhang [34] noted the degradation of graphene (and corresponding performance as a sensor), mounted on a SiO2 substrate, in the presence of X-ray irradiation and in the presence of reactive species such as oxygen or hydrogen. Sensor degradation needs to be considered when developing sensors for long-term use and increased radiation tolerance. 2.4.2 Molecular Detection In addition to graphene based radiation detection, graphene based sensors can be used for the detection of molecular chemical species. Highly sensitive sensors have application in the detection of gaseous radionuclides present in extremely low concentrations, which could be used for monitoring discharges from effluent
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treatment plants or the escape of radionuclides from containment in a waste disposal facility. Past development of sensors capable of detecting a single atom or molecule has been limited by their sensitivity. This is because the intrinsic noise due, to fluctuations in thermal motion of charges and defects, exceeds the signal from individual molecules, usually by many orders of magnitude. Schedin et al. showed that micron sized sensors made from graphene are capable of detecting individual events when a single gas molecule attaches to, or detaches from the graphene surface [35]. The adsorbed molecule changes the local carrier concentration in graphene one electron at a time, leading to step-like changes in resistance. Graphene is so suitable for the detection of single adsorption/desorption events due to the fact it has such a high conductivity and is an exceptionally low-noise electronic material. A review article recently highlighted the vast amount of research conducted on graphene-based gas detectors to date [36]. 2.5 Properties Relevant to Nuclear Applications The properties of graphene and related compounds that make it useful in the nuclear specific applications outlined above are summarised in Table 1. The properties have been grouped according to the particular applications. Table 1: Graphene Properties of Relevance to the Nuclear Decommissioning Industry
Application Properties Relevant to the Application
Water decontamination: Nano-filtration
• Structural functionalisation – incorporation of functional groups allowing nano-channels to form;
• High surface area – high water flux through nano-channels;
• Nano-channels only allow small solutes to filter through the material;
• Biodegradable – potentially lessened negative impact on the environment;
• Non-toxic (in this application) – again minimising impact on the environment and not contributing to water contamination.
Water decontamination: adsorption
• High surface area;
• Abundance of oxygen containing groups (negative charge) facilitate in absorbing radionuclides cations;
• 2D structure – maximises accessibility of the oxygen groups to give high adsorption capacity;
• Structural functionalisation – oxygen groups can be readily functionalised to improve selectivity and adsorption capacity;
• Dispersible in water;
• Biodegradable – no negative impact on the environment;
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Application Properties Relevant to the Application
• Non-toxic (in this application) – again minimising impact on the environment and not contributing to water contamination.
Isotopic separations • Electronic structure – the strength of the electronic
interactions between the graphene surface and hydrogen isotopes differ, allowing it to act as an isotopic sieve.
Composite materials: cement additives • High strength;
• Good mechanical properties;
• Dispersible in water;
• Structural functionalisation – oxygen containing groups form covalent bonds with the cement matrix;
• High thermal diffusivity;
• Binds to radionuclides to reduce the leaching properties of cement.
Composite materials: polymer composites • High strength;
• Good mechanical properties;
• Dispersible;
• Structural functionalisation – oxygen containing groups form bonds with the polymer matrix;
• High thermal diffusivity. Sensors: radiation detection
Exceptional electronic properties, which include;
• Low noise;
• Sensitive to changes in the local electric field created by a radiation induced event.
Sensors: molecular detection (e.g. monitor discharges)
Graphene-based sensors are capable of detecting events when a single gas molecule attaches or detaches from the graphene surface due to:
• Changes in resistance due to adsorption of molecules;
• High conductivity;
• Low noise.
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2.6 Summary Nuclear specific applications for graphene and related compounds have already been identified and could be used to support decommissioning and remediation work. To date graphene and related compounds have been investigated for water decontamination (molecular filtration, adsorption and isotope separations), as additives in cement and polymer composites and use in sensors for radiation and molecular detection. Some of the key properties of graphene and related compounds that make them useful in these applications are highlighted in Table 1 and include:
• Structural functionalisation – the incorporation of functional groups allows these compounds to form nano-channels, adsorb radionuclides and form covalent bonds with a range of materials. The latter allows graphene derivatives to be used an effective additive in composites;
• High surface area – the 2D structure means that accessibility of the functional groups is maximised, resulting in increased interaction with the surrounding environment which is required for applications involving adsorption and when incorporated into cement/polymer matrices;
• Dispersible in water – allowing graphene and related compounds to be used in water decontamination, as well as being readily dispersed within composite materials;
• Biodegradable and non-toxic – these compounds are potentially unlikely to cause additional problems to the environment and operatives, however this is also presented as a potential limitation to its use in Section 5.3;
• High strength – the favourable mechanical properties of these compounds could be used to enhance the mechanical properties of other materials when used as an additive;
• Electronic properties – these compounds are sensitive to changes in the local electric field, which could be created through interactions with the graphene surface and isotopes and molecules, or through a radiation induced event;
• Low noise – allowing graphene-based sensors to be used at room temperature, whilst displaying high resolution.
However, the properties of graphene and related compounds that are useful to the nuclear decommissioning industry are very application specific. Each application requires a unique set of properties that may not be favourable for other applications.
3 Graphene Research and Development Areas Section 2 focussed on the known, nuclear specific graphene related research conducted to date. This section, however, presents a wider review of graphene research, including non-nuclear graphene research areas. A desktop study was undertaken to identify research areas associated with graphene (and related compounds), and an assessment of their potential relevance to the nuclear decommissioning industry was made. The section provides an overview of the research teams, universities and research programmes worldwide that are undertaking graphene research, and their current and previous areas of interest.
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This includes information compiled by the NPL and UoM that have specialist knowledge in current graphene research areas, conduct research as institutions themselves, and participate in large collaborative programmes in graphene research. 3.1 Methodology The basis of the desktop study was to identify current graphene research from within the nuclear and non-nuclear research areas. This was achieved by reviewing published literature and funding awards. Various information sources were used as part of this review including:
• The Graphene Flagship; • Interviews with researchers at UoM; • Google Scholar and SciConnect; • US Department of Energy (DOE) funding database; • US National Science Foundation (NSF) database; • US Office of Scientific and Technical Information database; • Innovate UK; • A wider international literature review, including Asian research activities.
As previously mentioned, The Graphene Flagship has brought together a large European consortium with about one hundred and fifty partners in twenty-three countries. The partners represent academia, research institutes and industries, which work closely together in fifteen technical work packages and five supporting work packages covering the entire value chain from materials to components and systems. NPL reviewed ninety tasks (covering fifteen technical work packages and five supporting work packages) to highlight projects that are of relevance to the nuclear decommissioning industry. The UoM reviewed projects focussing on the key academic researchers in Asia, as well as reviewing the entire catalogue of Innovate UK awards and industrial collaborations and again identifying those projects relevant to the nuclear decommissioning industry. Regarding the US, a review was undertaken to search currently funded projects that contain the word “graphene”, including new projects awarded and funding renewals, from the US DOE and the US NSF websites. In total, 68 grants were provided by the US DOE search and 346 grants were provided by the NSF search. Each of the US DOE project abstracts were analysed and judged as to their relevance to the nuclear decommissioning industry. Given the larger number of US NSF funded projects, the abstracts were filtered using various keywords; e.g. “glass”, “composite”, etc.; and subsequently analysed and judged for their relevance. It was observed that the all of the funding of these projects from the US DOE and US NSF are associated with US universities and associated spin-out companies. Hence, a separate search of SciTech connect—a scientific search engine developed by the Office of Scientific and Technical Information (OSTI) within the US DOE was used to identify research publications associated with the seventeen US national laboratories funded by the US DOE. This provided 1651 hits, and were subsequently filtered on a laboratory-by-laboratory basis. It is noted that a number of results had no relevance to graphene and were filtered out by pattern matching “graphene” in either the title or abstract of the work. This filtering process yielded 266 publications.
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A complete list of unfiltered projects used in this literature review is contained in Reference [37], which contains a full list of research programmes from The Graphene Flagship, Innovate UK, US Doe, NSF and OSTI. This list was utilised for identifying the research areas of relevance, or potential relevance to the nuclear decommissioning industry. Research projects that were deemed to be relevant to the nuclear decommissioning industry were categorised into specific research area categories. These categories will be used later in Section 4, where correlations to the NDA decommissioning R&D requirements are made. A summary of the relevant and potentially relevant projects and publications from this review are presented in Table 2 in Section 3.2. Detailed results that provide a synopsis of each project/report are presented in Appendix A. 3.2 Summary From the literature survey outlined in Section 3.1, it is evident that there are numerous programmes of research that are relevant or potentially relevant to the nuclear decommissioning industry. In total, 119 projects/publications have been identified from the sources searched (Graphene Catapult, The Graphene Flagship, InnovateUK, US DOE, US NSF, OSTI and a wider international search including Asia). Table 2 provides a summary of the search results. The majority of the relevant, or potentially relevant projects centre on:
• Membranes – essentially selective barriers composed of GBM’s, with research often centred on desalination/waste water treatment and gas separation;
• Sensors – the use of GBM’s within sensors, predominantly gas-sensors, to detect molecules including water, oxygen, ammonia and nitrogen dioxide, at very low concentrations;
• Radiation detectors – another form of sensor, detecting ionising radiation using GFETs;
• Gas storage – utilising functionalised GBM composites and their porous 3D architectures with high surface areas for optimised gas adsorption and storage ; and
• Advanced materials – including cements, polymers, glasses, ceramics and coatings. Research centres on the incorporation of GBM’s into materials to form advanced composites with improved properties.
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Table 2: Number of Graphene Projects and/or Publications from Research in the UK, US and Asia that are Relevant to the Nuclear Decommissioning Industry
Source
Number of Projects/Publications
Relevant to the Nuclear Decommissioning Industry
Potentially Relevant to the Nuclear Decommissioning
Industry
Graphene Flagship Tasks 19 13
UoM Survey (Projects/ Publications) 13 22
US DOE Funded Projects 5 5
US NSF Funded Projects 7 14
US DOE Funded Publications 12 9
A more in depth presentation of the data is presented in Appendix A, while the full unfiltered output from the review is presented in Reference [37]. 4 Correlation Between the Identified Graphene Research
Areas and NDA Decommissioning Research and Development Needs
One of the key objectives of this project was to determine the potential applications of graphene (and its compounds) within the nuclear decommissioning industry. This section seeks to apply the knowledge acquired from previous sections which focussed on the useful properties of graphene and graphene research areas, to identify the correlations between the graphene research areas and the NDA estate decommissioning R&D needs. By identifying these synergies, further conclusions can be drawn as to the potential research gaps or areas of future opportunity for graphene research related within nuclear decommissioning. 4.1 Methodology An assessment of the NDA estate’s nuclear decommissioning R&D needs was undertaken by reviewing the NDA Technical Baseline document [2]. This document is based on the Site Licence Companies TBuRD submissions and discusses the NDA estate needs and opportunities for R&D in nuclear decommissioning. A summary of these R&D requirements and opportunities was then tabulated (Section 4.2 and Appendix B). The needs and opportunities were then assessed against the graphene research areas that were reviewed in Section 3 (and presented in full in Appendix A), to identify correlations between the identified graphene research and the NDA estate decommissioning R&D needs.
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4.2 NDA Decommissioning Research and Development Needs The NDA estate decommissioning R&D needs are categorised by ‘Strategic Theme’ and then by ‘Strategic Topic’ to provide a flowing structure to their requirements. The tabulation of these R&D requirements has therefore adopted this structure and is presented in Appendix B. Not all the R&D needs and opportunities are relevant to graphene research. R&D needs and opportunities deemed irrelevant include, “Technologies that would make NDAs uranics inventory more saleable” and “Improved statistical approach to monitoring programme”. These have been identified as needs and opportunities where the application of graphene technology would be unlikely to provide any feasible added benefit. Hence, some of the R&D needs listed in Appendix B have been struck-through and represent the NDA needs that were not deemed to be relevant to the scope of this project, or were repetitive from previous sections of the NDA Technical Baseline document [2]. 4.3 Identification of Correlations As described in Section 4.1, correlations between the NDA estate decommissioning R&D needs and opportunities, and current graphene research have been established and are presented in Table 3. This table lists all of the relevant NDA decommissioning R&D needs and opportunities that were identified in Reference [2] (and Appendix B). However, an additional column has been inserted into Table 3 showing the broad graphene research areas that could potentially be applicable to each of the NDA decommissioning R&D needs and opportunities. Further commentary with regards to the assignment of each correlation is provided in the following sub-sections. The NDA R&D needs that were deemed to be irrelevant (as indicated in Appendix B) have been removed from Table 3. Table 3 also highlights where there are currently NDA decommissioning R&D needs or opportunities, which currently have no applications within current graphene research areas, or require extensive further research to be developed. These will be discussed further in Section 4.4. The final column in Table 3 (Timescale for Application) gives the likely timescales for applying the identified graphene technology to each NDA R&D requirement. The timescales are denoted short, medium, or long term and are defined as follows:
• Short term: <5 years • Medium term: 5 - 20 years • Long term: >20 years.
For example, short term is applicable to graphene applications relating to Magnox reprocessing, where this is due to end in 2020. Long term application timescales generally relate to operational and decommissioning requirements, which could be >20 years from now. The timescales do not denote urgency, more the time in which the technology has to be developed for utilisation in these areas.
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Table 3: Identified Correlations Between NDA Estate Research and Development Needs and Graphene Research Areas
Strategic Theme Strategic Topic Research and Development Need Graphene
Research Industry/ Research Area
Timescale for Application
Spent Fuels – defines NDA approach to managing the diverse range of spent nuclear fuels for which we are responsible
Spent Magnox Fuel
Improved characterisation technologies that would provide Sellafield Ltd with a better understanding of the condition of the reprocessing facility could be required.
Sensors Short-term
Development of technologies to treat the small amounts of fuels left over once Magnox reprocessing operations cease.
No Direct Identification N/A
Further technologies to dry store and/or immobilise legacy Magnox fuels to manage materials held within Legacy Ponds and Silos (LP&S) at Sellafield.
Advanced Materials Short-term
Spent Oxide Fuel
Improved characterisation technologies that would provide Sellafield Ltd with a better understanding of the condition of the reprocessing facility could be required.
Sensors Short-term
Pond storage of spent oxide fuel is planned for a significant period. Therefore technologies that improve NDAs existing approach to treating pond water are of interest:
• Technologies that monitor spent oxide fuel and associated pond furniture under wet storage conditions will be required.
Radionuclide Remediation;
Membranes; Water Treatment;
Adsorbents; Gas Storage
Sensors
Short- to Long-term
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Strategic Theme Strategic Topic Research and Development Need Graphene
Research Industry/ Research Area
Timescale for Application
• In situ technologies that monitor the precursors of spent oxide fuel corrosion are of particular interest.
In the longer term technologies associated with drying, storage and disposal of spent oxide fuel are of interest to NDA.
No Direct Identification (potentially
Advanced Materials, for storage and
disposal)
Medium- to Long-term
Spent Exotic Fuel
Improved technical options for long-term storage of specific exotic fuels;
Advanced Materials Medium- to Long-term
Technologies associated with monitoring, storage, treatment and disposal of spent exotic fuels are therefore of interest.
Sensors; Radiation Detectors;
Advanced Materials;
Medium- to Long-term
Nuclear Materials – defines NDA approach to dealing with the inventory of uranics and plutonium currently stored on some of our sites
Plutonium Technologies for monitoring waste packages and stores that improve upon existing approaches are therefore of interest.
Sensors; Radiation detectors Short- to Long-term
Integrated Waste Management – considers how
Radioactive Waste
Reprocessing
There is a need to understand how the existing facilities will treat wastes from POCO of the
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Strategic Theme Strategic Topic Research and Development Need Graphene
Research Industry/ Research Area
Timescale for Application
NDA manage all forms of waste arising from operating and decommissioning NDA sites, including waste retrieved from legacy facilities
reprocessing facilities and how existing treatment facilities could be modified to manage new wastes. Some of the key areas of research include:
• Wasteform development (e.g. glass formulation) for vitrification of POCO HAL feeds;
• Options for treating effluents that allow decommissioning of existing facilities (e.g. SETP) to take place.
Advanced Materials
Membranes; Advanced Coatings; Water Treatment;
Radionuclide Remediation
Short- to Medium-term
Medium- to Long-term
There are also synergies with the interim storage of other packaged wastes (e.g. decommissioning waste). Some of the key areas of research include:
• Remote monitoring of waste packages (e.g. corrosion);
• Remote monitoring of stores (e.g. humidity).
Sensors; Energy/Energy
Storage (hydrogen capture)
Short- to Long-term
Legacy Facilities
Some of the key areas of research include:
• Remote monitoring of waste packages (e.g. corrosion, hydrogen evolution);
• Remote monitoring of stores (e.g. humidity, temperature).
Sensors; Energy/Energy
Storage (hydrogen capture)
Short- to Long-term
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Strategic Theme Strategic Topic Research and Development Need Graphene
Research Industry/ Research Area
Timescale for Application
Operational and Decommissioning Wastes
Some of the key areas of research include:
• Improved encapsulants (e.g. reduced cost, higher waste incorporation, increased security of supply, easier processability, increased compatibility with wastes).
Advanced Materials
Short- to Long-term
Liquid and Gaseous
Discharges
The liquid and gaseous discharges for decommissioning activities are more varied. Particularly at Sellafield, the variety can be challenging from a scheduling and compatibility viewpoint. Key areas of research include:
• Modular and mobile effluent treatment facilities to allow the decommissioning of existing effluent facilities or to manage short-term effluent requirements;
• In-line monitoring technologies to avoid the transport of samples and increase sampling interval.
Membranes;
Advanced Coatings; Water Treatment;
Radionuclide Remediation
Radiation Detection;
Sensors
Short- to Medium-term
Site Decommissioning & Remediation – defines NDA approach to decommissioning
Decommissioning
In situ characterisation to determine level of contamination:
• Portable versions of existing characterisation techniques;
• Non-destructive evaluation technologies.
Radiation Detectors; Sensors Short- to Long-term
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Strategic Theme Strategic Topic Research and Development Need Graphene
Research Industry/ Research Area
Timescale for Application
redundant facilities and managing land quality in order that each site can be released for its next planned use
Improved decontamination techniques:
• Increased efficiency and effectiveness;
• Reduction in secondary waste;
• Removal of heels and residues from process vessels.
Membranes; Advanced Coatings; Water Treatment;
Radionuclide Remediation
Short- to Long-term
Remote or enhanced operation for extreme conditions (e.g. high dose, confined spaces):
• Enhanced tools and techniques for air-fed suit decommissioning operations;
• Enhanced tele-operation (e.g. virtual reality and haptics);
• Robotics and autonomous systems.
Energy/Energy Storage;
Gas Storage; Advanced Electronics
Short- to Long-term
Land Quality Management; Site interim and End States; Land Use.
Improved groundwater monitoring:
• Increased automation to increase frequency of monitoring and reduce cost;
• Increased information (e.g. isotopic ratios, chemical speciation, improved limit of detection) to identify source of contamination;
• Increased information (e.g. in situ groundwater flux measurement) to improve predictions of movement of contaminants.
Advanced
Electronics; Advanced Materials;
Sensors;
Short- to Long-term
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Strategic Theme Strategic Topic Research and Development Need Graphene
Research Industry/ Research Area
Timescale for Application
Technologies and approaches for monitoring facilities and their contents over extended periods of C&M/deferral.
Sensors Medium- to Long-term
Techniques for early detection of leaks from existing facilities.
Advanced Coatings; Sensors;
Energy/Energy Storage
Short- to Medium-term
In situ remediation of contaminated ground:
o Techniques (e.g. bioremediation) that either reduce or limit the spread of contaminants and can be applied on sites with facilities still present.
Membranes; Advanced Coatings;
Energy/Energy Storage
Medium- to Long-term
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The main areas of graphene research that appear applicable to the overall NDA decommissioning R&D needs are:
• Sensors; • Advanced Materials; • Radionuclide Remediation; • Water Treatment; • Membranes; • Adsorbents; • Radiation Detectors; • Advanced Coatings;
The areas of graphene research that are potentially less applicable, but could be relevant in some way are:
• Gas Storage; • Energy/Energy Storage; • Advanced Electronics.
Further justification for the assignment of the above graphene research areas to the NDA decommissioning R&D needs is provided in the following sub-sections, with reference to some of the properties of graphene that enable it to provide added benefit in such areas. 4.3.1 Spent Fuels The NDA requirements for R&D for spent fuels centre on three main areas of graphene research/industry: Sensors; Advanced Materials and Membranes/Water treatment/Radionuclide Remediation. Projects referred to herein from Appendix A will be referred to by their project number, #, identifier. It is noted that there are potential limitations to the application of graphene technology/research identified to the NDA R&D requirements discussed below, including radiation tolerance, particularly in applications relating to spent fuel management. However, these limitations are discussed in Section 5. Spent Magnox and spent oxide fuel streams require further research into improved characterisation technologies to enable SLCs to have a better understanding of reprocessing facility conditions, which graphene sensor technology could potentially provide. Section 2 highlights the exceptional electronic properties of graphene (particularly its high sensitivity to changes in the electric field), which are also discussed in Reference [4], providing excellent sensor based capabilities. Both radiation and molecular detection sensors have been developed utilising graphene technology, which could be utilised by SLCs for facility condition characterisation. Appendix A includes multiple research projects, such as #3, #62 and #75, which describe sensors that can detect gases and achieve < ppm sensitivity for water, oxygen, ammonia and nitrogen dioxide, as well as other electrochemical type sensors. The gases may not be of direct relevance to SLCs facilities; however development of the technology could lead to the tuning of the materials to detect other gases with similar sensitivity. Magnox reprocessing will end in 2020, hence, the development of sensors for characterising and understanding the condition of Magnox reprocessing facilities would need to be undertaken in the near future.
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These sensors could also have potential applications in the monitoring of spent exotic fuels, as well as monitoring spent oxide fuel and associated pond furniture under wet storage. Graphene sensor technology could also be developed and tuned to monitor the precursors of oxide fuel corrosion. Appendix A includes reference to a research project, #102, which is focused on the development of graphene and 2D remote sensors for pools or waste storage, which has could have direct relevance to the monitoring of fuel corrosion under wet storage. The timescales for implementing sensors for the monitoring of spent exotic and oxide fuels would be medium to long term (5 - 20 years). The treatment of small amounts of fuels left over from Magnox reprocessing is not necessarily an area that current graphene research can be applied to. However the conditioning of such materials and development of materials to immobilise legacy Magnox fuels, could utilise graphene technology. Graphene has been shown to impart many beneficial properties to materials such as cements, polymers, ceramics and glasses, historically. The beneficial properties for some of these materials (particularly those for graphene doped polymers) are highlighted in Section 2.3. These graphene-based composites display high strength, good mechanical properties, and high thermal diffusivity. Graphene doped polymers have shown improved leaching performances over non-doped polymers, and due to the adsorptive properties of GO, the addition of GO has the potential to also improve the leaching properties of cements. Cements, polymers, ceramics and glasses have all been used previously in immobilisation and encapsulation of nuclear waste. Therefore graphene doped advanced composite materials with enhanced properties, may be ideal for use in such a role. Appendix A includes multiple research projects relating to graphene doped polymers (including #26, #27, #46, #54, #55, #57), cements (#96), ceramics (#33 and #42) and glasses (#58), with many focussed on the beneficial properties for applications in the nuclear decommissioning industry. These materials also have potential applications in the conditioning and disposal of spent oxide and exotics fuels, and long-term storage of specific exotic fuels. It is further recognised that the advanced cement material, for example, could be used for construction purposes, with application in future dry storage facilities for spent nuclear fuels and nuclear waste in general. The NDA requirement for research into spent oxide fuel pond water treatment, and also the treatment of radioactively contaminated water or effluent in general, is likely to be an area where application of graphene technology could provide added benefit to the NDA. Graphene materials, particularly GO which can be fabricated into a membrane with relative ease or dispersed into water, possesses properties enabling it to perform nano-filtrations and isotopic separations and, adsorb target cations and also selectively filter/separate tritium. Sections 2.1 and 2.2 document these properties and include some of the research projects these materials have been currently involved in. For example, the potential removal of Tc99 through nano-filtration [7], adsorption and removal of toxic and radioactive long-lived radionuclides from water [8], and isotopic separation of hydrogen isotopes [20]. The deployment of such materials at Sellafield for the treatment of radioactively contaminated water could be highly beneficial in the removal of radionuclides, with the added benefit of being able to target specific radionuclides. It has been highlighted that a recurring problem in both aqueous effluent treatment and environmental decontamination is poor selectivity and that new highly selective materials are required.
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Appendix A includes several further examples of research projects looking at Membranes, Water Treatment and Radionuclide Remediation (including #2, #4, #25, #50, #56, #63, #85 etc.) showing the promising potential for the use of GBMs in this nuclear decommissioning application. Appendix A also includes examples of the use of GBMs for water desalination purposes, which have been highlighted as having relevance to nuclear decommissioning due to the similarity in the application to radionuclide remediation in contaminated waters, including projects #80 and #81. 4.3.2 Nuclear Materials The NDA decommissioning R&D requirements for nuclear materials, specifically plutonium are related to technologies for monitoring waste packages and stores. Again, it is noted that there are potential limitations to the application of graphene technology/research identified, such as radiation tolerance particularly in applications relating to nuclear material management and these limitations are discussed in Section 5. The graphene research areas that correlate with this requirement are focussed on Sensors and Radiation Detection, which were discussed in Section 4.3.1. Graphene-based systems could offer potential benefits over current systems due their high sensitivity offering low limits of detection. Particularly radiation detectors, as previously, mentioned there is a need for inexpensive, low-power, size-scalable detection devices, which are exceptionally sensitive to X-rays, gamma-rays, and neutrons, which could be used for detecting the presence of nuclear material and radionuclides. Further research may be required to tune the materials to detect the required chemical components or types of radiation or to provide in-line detection. Appendix A shows the extent of research being conducted in this field. The timescales for applying graphene based sensors and radiation detectors to this strategic topic span short term through to long term (<5 years to >20 years, Table 3). 4.3.3 Integrated Waste Management The NDA integrated waste management R&D requirements for radioactive waste is split into “Reprocessing”, “Legacy Facilities” and “Operational and Decommissioning Wastes”. The requirements for “Reprocessing”, again correlate well with the research areas of Advanced Materials and Water Treatment/Membranes/Radionuclide Remediation. The requirement for the development of vitrification wasteform for POCO HAL feeds could utilise the Advanced Materials graphene research, which was discussed in Section 4.3.1 and include the concept of deploying graphene based composite materials for waste conditioning. Appendix A includes a research project relating to the development of novel advanced glasses (#58), which could be directly relevant to vitrification of POCO HAL feeds. As indicated in Table 3, a short to medium timescale (5 – 20 years) would be applicable for the development of advanced graphene materials in vitrification.
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Regarding options for the treatment of effluents highlighted in the “Reprocessing” section of Table 3, it is thought that the research discussed in Section 4.3.1, relating to graphene’s applications in contaminated water and effluent treatment could be relevant. As previously mentioned, Appendix A includes many relevant research projects to this area. However, project #107 which relates to researching smart filter membranes adopting advanced coatings may be of specific relevance to this requirement. The Smart filter membranes are based on graphene and have been tested in desalination trials in aqueous media and the project focus is to expand into applications within nuclear decommissioning/desalination. Applications involving water and effluent treatment have a longer application window, ranging from medium to long term (5 - >20years). The NDA R&D requirements for both “Reprocessing” and “Legacy Facilities”, for research into remote monitoring of waste packages and stores, is again applicable to the graphene research area of Sensors. As discussed previously, this graphene research area for the use in SLC monitoring applications has been discussed in Section 4.3.1. In addition, Appendix A contains research projects relating to hydrogen capture (#70) which could be applied to the monitoring of corrosion/hydrogen evolution of wastes. Moreover, sensors which monitor gaseous water (#3) could potentially be applied to monitoring humidity. The NDA R&D requirements for “Operational and Decommissioning Wastes” involve research into improved encapsulants. The graphene research area of Advanced Materials has direct relevance for this requirement and is discussed in Section 4.3.1. Briefly, new graphene-based composites involving polymer and cement may have beneficial properties for waste conditioning and packaging. The NDA R&D requirements for “Liquid and Gaseous Discharges” correlate well with the research areas of Water Treatment/Membranes/Radionuclide Remediation and Radiation Detectors/Sensors. The requirement for research into modular and mobile effluent treatment facilities could be complemented by the graphene research areas of Water Treatment/Membranes/Radionuclide Remediation, which was discussed in Section 4.3.1. The mobile aspect of these facilities could be complemented by the lightweight nature of graphene and ability to prepare GO membranes to a required size, suitable for a mobile device. The requirement for research into in-line monitoring technologies correlates well with the graphene research area of Radiation Detector and Sensors, as discussed in Section 4.3.1. The use of graphene brings the benefits of a higher sensitivity, though the long-term ionising radiation tolerance of graphene should be considered further. This aspect is to be considered in depth as part of project #39 in Appendix A. 4.3.4 Site Decommissioning and Remediation The NDA site decommissioning and remediation R&D requirements are split into the strategic topics, “Decommissioning”, “Land Quality Management”, “Site Interim and End States” and “Land Use”. The predominant graphene research areas that correlate well with these requirements are Sensors, Radiation Detectors, Membranes/Water Treatment/Radionuclide Remediation, Advanced Coatings, Energy/Energy Storage and Advanced Materials/Electronics.
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The NDA requires further research into in situ characterisation to determine levels of contamination during site decommissioning, which correlates well with the graphene research area of Radiation Detectors and Sensors. Discussion surrounding these research areas has been documented in Section 4.3.1. However, it can be further embellished to consider the portability aspects that NDA require. As described in Section 2, graphene is a lightweight yet mechanically strong material which is ideal for manufacture of portable equipment, both for the actual sensor electronics required and potentially also for the casing of the device. A further more abstract link is to the graphene research area of Energy/Energy Storage, which could be applied to this role in the form of portable power supplies for these devices. However this is likely to require significantly more development. Research projects, such as project #117 in Appendix A, are looking to combine graphene with materials such as steel, as a charge collecting material in batteries and other advanced energy storage devices. Successful utilisation of this technology could allow for improvements in performance as well as significant cost reduction in batteries and supercapacitors alike. Short to long timescales (<5 years to >20 years) would be applicable to the development and utilisation of these applications. Research into improved decontamination techniques are also required which correlates well with the graphene research areas of Membranes, Advanced Coatings, Water Treatment and Radionuclide Remediation. The application of these graphene research areas for decontamination and removal of radionuclides from contaminated solutions has been documented in Section 4.3.1, with the increased effectiveness and efficiency due to the enhanced selectivity of the graphene materials. The NDA are also seeking to minimise secondary waste in these techniques, which the employment of advanced coatings for filters such as those being developed in Appendix A, project #107, can offer. As the radionuclides are trapped onto a graphene-based membrane, the filter could be used for longer rather, potentially reducing secondary waste generation. Graphene-based research into Energy/Energy Storage and Gas Storage is currently one of the most prominent sectors for graphene research and could be applied in devices intended for remote or enhanced operation in extreme conditions. GBMs have shown the potential to be used in hydrogen cells (Appendix A, #77) and as charge collecting materials for use in batteries and other advanced storage devices (Appendix A, #117). This technology could be utilised in portable devices, such as handheld/portable monitoring devices (as discussed in Section 4.3.4) and also in equipment such as Remotely Operated Vehicles (ROVs). Applications for ROVs in decommissioning can vary greatly. However increased battery performance/power storage may be beneficial to ROVs with high energy consuming components (such as tooling for decommissioning, including dismantling and disrupting equipment). Such tooling may drain battery life, preventing the ROV from operating over long timescales. Similar to this area is the further development of the Advanced Electronics graphene research area. The NDA also requires further research into improved groundwater monitoring for site remediation applications. In terms of groundwater monitoring, an increase in automation could be brought about by application of advanced graphene-based electronics and materials. Utilising graphene sensor technology to increase information obtained during monitoring, identifying contaminants and predicts their movements, is a promising area. Further to the previous discussion surrounding the
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use of graphene-based sensors (Section 4.3.1), graphene sensors could potentially be utilised in the future for the determination of chemical speciation. Appendix A contains a research project (#75) that is developing advanced electrochemical sensors, with applications in the nuclear decommissioning industry, which could determine information relating to contaminants based on their electric potential. The use of graphene sensor technology has also been previously discussed in Section 4.3.1 for use in monitoring of facilities and waste packages, and so could be applicable for waste package condition monitoring and inspection. Techniques for early detection of leaks from existing facilities could also utilise the graphene research area of Sensors. This could also be complemented by the application of the graphene research area of Energy/Energy Storage and Advanced Coatings. Appendix A contains projects, such as #77, which discusses the use of GBMs tritium capture, which could be useful in detecting tritium permeation. Appendix A also highlights a project, #91, which is researching the use of reduced GO as a cheap coating sensor to measure radiation leaks, which again would be directly applicable. Project #77 in Appendix A, is also potentially relevant for applications intended to reduce or limit the spread of contaminants during in situ remediation of contaminated ground, particularly for tritium contamination. GBMs could be utilised to capture tritium being emanated and hence reducing or limiting the spread of tritium. Appendix A contains other projects looking at gas storage, particularly in the Energy/Energy Storage graphene research area, which could have cross-over applications in the trapping of radioactive gases. The graphene research area of Membranes and Advanced Coatings could correlate well with the application of reducing or limiting the spread of contaminants, particularly if the GBMs could be deployed around the perimeter of the contaminated ground. Section 4.3.1, discusses the ability for graphene membranes and coatings to remove Tc99 [7], remove toxic and radioactive long-lived radionuclides [8], and isotopic separation of hydrogen isotopes to potentially remove tritium [20], in aqueous systems. These could be potentially utilised in contaminated ground environments where the groundwater flow transports soluble contaminants, such as Tc99 as pertechnate. 4.4 Identification of Research Gaps and Opportunities From reviewing Table 3, it can be seen that the vast majority of the NDA decommissioning research and requirements broadly correlate with the graphene research areas identified in Appendix A. However, some gaps in the NDA requirements were identified during the above assessment are discussed in Section 4.4.1. Furthermore, a number of potential opportunities have been identified and will be discussed further in Section 4.4.2. 4.4.1 Potential Research Gaps Two of the NDA requirements from Table 3 have been identified as potential gaps. A potential research gap is defined as an NDA R&D opportunity or need where the application of graphene technology could potentially provide feasible added benefit, but does not currently correlate with any of the research projects identified. Research
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gaps therefore differ from irrelevant research areas, which were discussed in Section 4.2. Irrelevant research areas are those where graphene technology is not thought to provide any benefits (e.g. making the uranics inventory more saleable and improving statistical approaches). The two potential research gaps include: Spent Fuels: Development of technologies to treat the small amounts of fuels left over once Magnox reprocessing operations cease;
• There are currently no graphene research areas that have been reviewed that have potential applications in the treatment of fuels, i.e. in such roles as fuel reprocessing.
Spent Oxide Fuel – In the longer term technologies associated with drying, storage and disposal of spent oxide fuel are of interest to NDA;
• There are currently no graphene research areas that have been reviewed that have potential applications in the drying of fuels.
• However, Advanced Materials could be utilised in the future storage of spent oxide fuels, in the manufacture of waste containers or dry fuel storage casks.
• It has already been discussed that Advanced Materials may have a role in waste encapsulation/immobilisation, which could also be utilised for spent oxide fuel disposal.
Further research could be conducted into the application of graphene in these areas. However, this may not be necessary given the maturity of existing fuel treatment technologies. Therefore, graphene based research may not yield any significant benefits beyond those already provided by existing fuel treatment technologies. 4.4.2 Potential Opportunities In addition to the research correlations identified in Section 4.3, opportunities for further graphene research have been identified that could provide benefit to the NDA estate in ways not considered previously. Many of these opportunities would need to be developed further with a nuclear decommissioning interest in mind. As highlighted in Section 4.3, the graphene research area of Advanced Materials such as cements, polymers, ceramics and glasses, could be utilised in the conditioning and immobilisation of nuclear and radioactively contaminated wastes. Further research into this, specifically for the encapsulation and immobilisation of these wastes could be a great opportunity to explore. Furthermore, combining these immobilising/conditioning materials within waste containers lined with graphene membranes could be an opportunity for further research. Waste containers lined with GO membranes that can capture radionuclides and/or perform isotopic separations to prevent radioisotopes from migrating out of the waste container could be advantageous in a geological repository environment. This may be particularly relevant after ground water infiltration has occurred within the waste packages and could minimise the release of radionuclides into the environment. GBMs could also be used in the filters of vented waste containers, to again minimise radionuclide
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release, particularly of gaseous radionuclides. Such research could be complemented by the research project #56 discussed in Appendix A, which aims to research GBMs and understand their impact on microbial populations used in wastewater treatment. This in turn may overlap with the interactions between water, microbes, and graphene-based wastes in a repository environment. Research into graphene’s long term radiation hardness and potential environmental effects should be also considered (examples of projects listed in Appendix A include #68, #89, #93 and #94). Graphene research has also been focused on the development of corrosion resistant coatings. Project #111 in Appendix A aims to research the potential of graphene in fire retardant and protective coatings. This could certainly be beneficial to machinery and tooling employed in corrosive decommissioning environments, such as the caustic ponds used for wet storage of nuclear waste, or waste containers in a potentially high pH cementitious geological repository environment, where corrosion is a significant factor. Utilising a protective coating could prolong the life of machinery, tooling and waste containers. The latter potentially slowing the corrosion and failure of waste containers in a geological repository environment. Graphene is also being researched for use in oil products, to provide enhanced lubrication and hence reduce the wear/extend the life of components. This could again be beneficial to the NDA estate, in improving the lifetime of machinery and tooling used in nuclear decommissioning and lowering secondary waste arisings. 5 The Potential Limitations of the Use of Graphene in
Nuclear Decommissioning Applications Although graphene and other GBMs could potentially provide benefits to the nuclear decommissioning industry, there are also limitations and barriers to the use of these materials. These are discussed in the following sub sections. 5.1 Cost The cost of producing graphene for commercial applications varies greatly by mass, depending on its physical form (such as powder/film), its chemical form (pure graphene, GO or other functionalised material), or by its density. The price variation is brought about in part due to the method of manufacture (as discussed in Section 5.2). Table 4 presents a comparison of some commercial prices for graphene and related compounds, with prices accurate as of February 2017.
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Table 4: A Comparison of Commercial Prices for Graphene in Different Forms
Supplier Form and Amount Price
Graphenea Graphene Oxide (0.5 mg/mL, Water Dispersion 250 mL) £38.74
Graphenea Graphene Oxide Powder (1 gram) £82.64
Graphenea Easy Transfer: Monolayer Graphene on Polymer Film (1 cm x 1 cm) £61.98
Sigma-Aldrich Graphene powder, bulk density 0.0215, weight 6 g, platelet planar size 0.3-5um £485.00
Cambridge Nanosystems CamGraph Graphene Powder (1 g) £185.00 – £240.00
(depending on density) The prices in Table 4 vary greatly, with graphene in its pure powdered form being the most expensive. This is due to its high manufacturing costs. The application and hence form of graphene required and the resulting benefits will determine whether the cost is prohibitive. Applications requiring pure powdered graphene will inherently cost more than those requiring less pure graphene. Cost as a limitation will also depend on the amount of graphene required in the application, for example the amount of graphene required to dope an advanced cement or polymer, will affect the cost for the production of the material. Overall the cost of graphene is decreasing, this is due to the increasing number of manufacturing facilities and manufacturing processes becoming more scalable, specifically in CVD and epitaxial growth on silicon carbide (see Section 5.2).
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5.2 Manufacturing Scale Up The properties of graphene are strongly affected by its form and defect structure. The latter is dependent on the fabrication method, interactions with the substrate and environment. It should also be noted that many properties of graphene are not necessarily maintained as the material is scaled-up and is thus a limitation [4]. Table 5 presents the advantages and disadvantages of each graphene manufacture/scale up by method. Table 5: Advantages and Disadvantage of Graphene Scale Up by Method
Graphene Manufacturing Method
Advantages Disadvantages
Micro-mechanical exfoliation
• High quality, single crystals of monolayer graphene with micron sizes;
• Method can be applied to other layered crystals.
• Not scalable.
Chemical Vapour Deposition
• Large area growth of single-layer graphene, >50 cm2;
• Roll-to-roll production of graphene.
• Polycrystalline, defects e.g. pin-holes created;
• High costs; • High process
temperatures (~1000 °C).
Liquid phase exfoliation (includes ultrasonic, shear and electrochemical exfoliation)
• Scalable processes; • Easy to realise; • Moderate yields
(dependent on method); • Nanometre to micron sizes; • Low costs.
• Non-uniformity of nanosheets;
• Impurities; • Ultrasonic and shear
typically yields low concentrations;
• Requires multiple cycles.
Epitaxial Growth on silicon carbide
• High quality, thin films (several microns).
• Low yield; • High cost; • Requires high
temperatures (1500 °C).
Oxidation of Graphite to form GO
• High yield; • Scalable; • Material can be further
functionalised; • Dispersed in water; • Insulating material.
• Hazardous reaction including strong acids and oxidants;
• Requires excessive water washes;
• Expensive.
Reduction of GO to form RGO
• High yield; • Scalable; • Variety of reducing
methods.
• Until recently, difficult to effectively remove all oxygen groups;
• Defects.
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Table 5 shows that generally, methods that produce high quality, single crystals of pure graphene are not scalable [4]. This may be for technical reasons, or for financial considerations. However as discussed in Reference [4], pure graphene is not always required for materials with certain desired properties. Though applications where it is required, there are currently no available methods for large scale. This could be a limitation to graphene’s use in the nuclear decommissioning industry. For example the production of advanced sensors and detectors generally requires graphene that is synthesised by the manufacturing methods CVD and epitaxial growth on silicon carbide (SiC), which currently have high associated cost, though those are decreasing steadily. The cost of producing SiC wafers is not an obstacle anymore, however the cost of producing graphene layers from these wafers will remain relatively high until production is scaled up, which is possible in the future. 5.3 Environmental Safety Impacts A number of literature reviews have been conducted into the environmental and safety impacts of GBMs. It is recognised however, that due to the relative immaturity of graphene and graphene technology, the long term effects of these materials on humans, wildlife and the environment are generally not yet known. A review by Pinto et al assesses the biocompatibility of GBMs [38], which could be relevant to the nuclear decommissioning industry if GBMs become released into the environment, or come into contact with humans and wildlife. Studies have shown that mammalian cell viability decreases slightly after exposure to GBMs. The in vivo effect of GBMs were found to depend on the physical–chemical properties, concentration, time of exposure, and administration route, and also on the characteristics of the animals used. Most studies reported no occurrence of adult animal death. However, it is noted that there are some reports of GBMs accumulation and histological findings associated with inflammation, and, more rarely, fibrosis. The encapsulation of GBMs in a matrix has shown a potential reduction in toxicity and some reports show potential antibacterial properties of GBMs [38]. A paper by Zhao et al assesses the impacts of graphene in the aquatic environment [39], which again could be relevant if these materials are used in the nuclear decommissioning industry. Upon exposure in aquatic environments, GBMs have shown to have adverse impacts on aquatic organisms (e.g., bacteria, algae, plants, invertebrates, and fish). GBMs internalised in the cells of biota through direct penetration can cause oxidative stress, mitochondrial dysfunction, and DNA damage [39]. It is also seen that GBMs transform and/or degrade in the aquatic environment, such as the transformation of GO, to reduced GO and the degradation of GBMs upon exposure to UV irradiation and/or biota. A review by Arvidsson et al [40] assessed the potential environmental and health risks of graphene. The results from this study indicated that graphene could exert a considerable toxicity and that considerable emission of graphene from electronic devices and composites are possible in the future. The effects include physical damage to cell membranes, attachment to cell membranes and also signs of cell apoptosis (non-programmed cell death) [40]. It was also suggested that graphene is persistent and has a long residence time in the environment. However, the report caveats this statements with the stance that further work needs to be undertaken into
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graphene’s toxicity, particularly with a risk perspective taking into account aspects including:
• Workplace emissions and exposure; • The fate of graphene in environmental media; • The physical shape of graphene in environmental media.
From the above information it can be seen that graphene could pose a potential risk to humans, wildlife and to the environment. If utilised in an advanced material as a composite, it appears that this could be much less of a risk than applications of pure graphene [38]. Taking into account all of the information, it is seen that further work is required to fully assess the safety risks of graphene to humans, wildlife and the environment, and assessments into the degradation components of GBMs and their potential hazards is required. 5.4 Regulatory Concerns The main limitations to the nuclear industry are related to how the material will be registered e.g. through the European Union regulation of Registration, Evaluation, Authorisation & restriction of CHemicals (REACH)1, or an alternative registration route. Currently there are no UK or international regulations relevant to good practice for graphene based technologies, or clearly defined health and safety requirement for handling these materials [41]. This poses a threat to the development of graphene technologies and the safety of both workers and the public. Though recently the European Commission has launched a public consultation regarding the benefits, risks, concerns and awareness of technology. From a nuclear decommissioning perspective it is important that there is an understanding and awareness of the safety implications of graphene technologies within the nuclear sector to enable efficient regulation of the industry. It is acknowledged that the nuclear industry may be indirectly exposed to graphene and related materials. For example, through introduction of GBMs in materials such as oils and steels doped with graphene. These materials may already be used, but the industry may be unaware of due to the commercial protection placed on the formulations sold by the suppliers. It is further understood that the Office for Nuclear Regulation (ONR) is intending to develop a process for approving new materials and new technologies intended for use in the industry, which will be of relevance to implementation of graphene into the nuclear decommissioning sector. 5.5 Lack of Standardisation Standardisation is required to ensure clear product specifications and product safety. For large scale commercialisation the materials standards, regulations, supply availability and fair price must be obtained [41]. There are no current materials standards that companies must comply with in relation to graphene. This results in an
1 REACH aims to provide high level protection to human health and the environment. It also aims to make the people who place chemicals on the market (manufacturers and importers) responsible for understanding and managing the risks associated with their use.
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adverse effect on the development of the sector as end-users, regulators and insurers cannot assess product quality of GBMs. Nor can they obtain guidance on material safe usage or adopt any Health and Safety standards [42]. International standardisation will be crucial for what could be a worldwide market, though no international standards have yet been published for graphene. There is currently activity in this area, in both the International Organization of Standardization (ISO) and the International Electrotechnical Commission (IEC), with several standards currently under development [42]. Standardisation will also ensure the properties of the materials produced are consistent, which is important to the application of GBMs in the nuclear decommissioning industry. This is in part due to the fact the properties that make a GBM attractive for one application may mean that it is unsuitable for another application. For example, whilst the electronic properties of pure graphene (low noise, high conductivity and highly sensitive to changes in the local electrical field) make it an attractive material for sensors and detectors, the inert nature of the material is unlikely to be as useful in radionuclide adsorption or composite materials. Therefore, the properties of graphene and related compounds that are useful to the nuclear decommissioning industry are very application specific and standards are required to ensure these properties are correct and consistent for each different application. There is a notable program of R&D at NPL and the Graphene Flagship aiming at the development and validation of rapid, accurate, preferably in-line measurement protocols and instrumentation. These will be developed for structural, physical and chemical characterisation and quality control of 2D materials produced on an industrial scale, which will lead to new standards and measurement services. 5.6 Radiation Tolerance As outlined in Reference [4], graphene has been shown to degrade when exposed to gamma, alpha and beta radiation [43, 44, 45], with severe lattice damage being observed at low energies (80 keV for beta particles and 1.5 MeV for alpha particles). However, encapsulation of graphene within devices has been shown to improve the radiation hardness, hence maintaining the performance and stability of the material. Such improvements in the radiation hardness have been demonstrated for graphene based semi-conductor devices [43, 46]. To be utilised in the nuclear industry graphene is likely to need to withstand exposure to ionising radiation, at least to an extent where its properties are unaffected, to allow it to fulfil its function. The application of graphene in Advanced Materials is likely to be effective in terms of radiation tolerance, due to graphene’s improved radiation tolerance in composite materials. The use of pure graphene in Sensors could be affected by the materials lack of radiation tolerance. However it is likely the device that the pure graphene is constructed into will offer some protection/shielding, meaning the graphene may not be directly exposed to the radiation. Again, like most of the limitations discussed, further research into graphene’s radiation tolerance is required. Appendix A documents a number of projects related to this area which will hopefully provide further information in the coming future.
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6 Conclusions This report has identified a number of key correlations between the NDA decommissioning R&D needs and graphene research areas. Hence, broader research programmes being undertaken in academia and industry, could provide added benefit to the NDA estate in the future of nuclear decommissioning. The desktop review of the graphene research areas provided a comprehensive outlook of current graphene research. The categorisation of the research projects into different industry/research areas facilitated the high level correlation of the graphene research areas to the NDA decommissioning R&D requirements. The graphene research areas that formed the predominant links with the NDA R&D requirements included, Sensors/Radiation Detectors, Radionuclide Remediation/Water Treatment/ Membranes/Advanced Coatings. The timescales for implementing the identified graphene research/technology varies depending on the intended application within the nuclear decommissioning industry (Table 3). For example, graphene applications related to fuel reprocessing (such as Magnox) would likely need to be implemented within the next 5 years. Applications relating to decommissioning may be less time constrained with the timescale for application being within 20 years, or longer. Discussions and arguments have been put forward to explain the correlations between the graphene research areas and NDA requirements. Many of these discussions and arguments hypothesised using the knowledge acquired previously about graphene’s properties, helping to illustrate the potential added benefit graphene could provide to the nuclear decommissioning industry. A few of the NDA requirements could not be synergised with a graphene research area, though this was very much the minority and were listed in Section 4.4.1. The limitations to the use of graphene in the nuclear decommissioning industry were also assessed. It was identified however, that further research would be required to confirm the most significant limitations, especially regarding long term effects of graphene and GBMs to human/wildlife health and the degradation of the material. The cost and the scale up of manufacture is a limitation depending on the type of graphene material required, with pure graphene currently being harder to scale up and costing more to produce. Though as described, the purity of graphene does not always relate to its performance, as this is application dependent. The potential toxicity of graphene is a potential major limitation, especially in aqueous environments, and if graphene cannot be proven safe to use in such environments then this limits the applications it can be used for in the nuclear decommissioning industry. This would particularly affect its use in effluent treatment or being used in immobilisation/encapsulation in waste packages destined for a geological repository. The regulation and standardisation of graphene are inherently linked, as standards need to be formed to ensure compliance with regulations, particularly those of the ONR, to enable graphene’s use in the nuclear decommissioning industry. However, international standardisation is currently under development, which could prevent these factors from being major limitations. The last potential limitation considered was radiation tolerance. This aspect is important, as graphene research indicates
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that graphene is generally used in a composite form, reducing this factor as a limitation. 6.1 Key Synergies Identified The key collations and opportunities with respect to the nuclear decommissioning industry are:
• Advanced Materials – These include advanced polymers, cements, ceramics and glasses. These could be utilised in the conditioning/immobilisation of nuclear wastes, as well as in construction of modern devices or buildings/facilities. The benefits of including GBMs in composite materials include enhanced mechanical and leaching properties. The use of graphene in a composite could also improve graphene’s radiation tolerance and could potentially lower its toxicity by being chemically incorporated into the composite matrix and reducing its likelihood of migration into the surrounding environment. Graphene used in composites is unlikely to be required in its pure form, with GO being more applicable which has greater scale-up potential and lower costs.
• Membranes – These could be utilised in effluent treatment and potentially incorporated into future waste containers, to minimise radionuclide leaching. The major benefit to graphene in this role is its selectivity.
• Sensors/Radiation Detectors – These could be utilised in numerous roles as identified in Table 3. The impressive electronic properties of graphene potentially lend itself to the development of enhanced Sensors/Radiation Detectors for the use in the nuclear decommissioning industry. The radiation tolerance and costs for manufacture will need to be further considered, however, in terms of the sensitivity that could be offered these are worth further investigation.
7 Recommendations
1. Further consideration of the research gaps identified in Section 4.4.1, which relate to Magnox fuel (treatment of small amounts of fuels left over once Magnox operations cease) and spent oxide fuel (technologies associated with drying, storage and disposal). Initial assessment indicated that none of the existing graphene research areas correlated with these NDA requirements. However it should be considered whether graphene technology is needed to fulfil these requirements, when other technologies have been or are being developed to satisfy these requirements.
2. It is further recommended that the graphene research areas identified as being relevant to nuclear decommissioning applications (Section 4) are investigated further. This could be achieved through appropriate mechanisms to support early development, such as feasibility studies with Innovate UK, DRP projects or PhD projects, and could include:
• Trials to assess the suitability of graphene doped advanced materials for nuclear waste immobilisation/encapsulation;
• Trials to assess the incorporation of graphene membranes into RWM approved waste containers and assessment of their radionuclide retention;
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• Manufacture of radiation resistant graphene materials for use as in-situ radiation detectors/leak monitors;
• Trials to assess the gas storage capabilities of graphene materials; • Trials to assess the performance of graphene based energy storage
devices and their ability to improve operations that require the use of remote surveillance equipment.
3. In addition to the technical applications noted above, the NDA could maintain
a watching brief on the limitations relating to the use of graphene in the nuclear decommissioning industry. These limitations include cost, manufacturing scale-up, environmental and safety, regulation and standardisation (Section 5).
4. Finally it is recommended that the NDA proactively follow a number of
journals, research groups, funding bodies and conferences (such as those suggested in Ref. [4]) to keep abreast of up to date graphene research and technology. Due to the rapid development of graphene research and technology, the content of this report has a lifetime. Therefore, it is recommended that this document is reviewed and updated biennially to ensure that the information represents the latest graphene research and technology. Conducting this review biennially would also coincide with the cycle of the Graphene Flagship, aligning well with the review and update process. Ultimately further advances in graphene and related materials, specifically targeting nuclear decommissioning, would require close interaction between the graphene researchers, nuclear engineers and regulatory authorities. This means targeted joint R&D projects involving multi-disciplinary teams.
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8 References 1 NDA, Research and Development – 5 Year Research and Development Plan,
Issue 1, December 2013
2 NDA, Research and Development – NDA Technical Baseline, Issue 1, October 2016
3 Clarivate Analytics, Web of Science™ – The world’s most trusted citation index covering the leading scholarly literature
4 P. Davies, A. Tzalenchuk, P. Wiper and S. Walton, Summary of Graphene (and Related Compounds) Chemical and Physical Properties, NS4145-500-001, Issue 1, November 2016
5 R. R. Nair, H. A. Wu, P. N. Jayaram, I. V. Grigorieva and A. K. Geim, Unimpeded Permeation of Water Through Helium-Leak-Tight Graphene-Based Membranes, Science, 335, 442-444, 2012
6 R. K. Joshi, P. Carbone, F. C. Wang, V. G. Kravets, Y. Su, I. V. Grigorieva, H. A. Wu, A. K. Geim and R. R. Nair, Precise and Ultrafast Molecular Sieving Through Graphene Oxide Membranes, Science, 343, 752-754, 2014
7 C. D. Williams and P. Carbone, Selective Removal of Technetium from Water Using Graphene Oxide Membranes, Environ. Sci. Technol., 50, 3875-3881, 2016
8 A. Y. Romanchuk, A. S. Slesarev, S. N. Kalmykov, D. V. Kosynkin and J. M. Tour, Graphene Oxide for Effective Radionuclide Removal, Phys. Chem. Chem. Phys., 15, 2321 - 2327, 2013
9 Y. Sun, S. Yang, Y. Chen, C. Ding, W. Cheng and X. Wang, Adsorption and Desorption of U(VI) on Functionalized Graphene Oxides: A Combined Experimental and Theoretical Study, Environ. Sci. Technol., 49, 4255, 2015
10 Z. Li, F. Chen, L. Yuan, Y. Lian, Y. Zhao, Z. Chai and W. Shi, Uranium (VI) Adsorption on Graphene Oxide Nanosheets from Aqueous Solutions, Chem. Eng. J., 210, 539, 2012
11 G. Lujaneine, S. Semcuk, I. Kulakauskaite, K. Mazeika, D. Valiulis, R. Juskenas and S. Tautkus, Sorption of Radionuclides and Metals to Graphene Oxide and Magnetic Graphene Oxide, J. Radioanal. Nucl. Chem., 307, 2267, 2016
12 X. Wang, Z. Chen and X. Wang, Graphene Oxides for Simultaneous Highly Efficient Removal of Trace Level Radionuclides from Aqueous Solutions, Sci. China Chem., 58, 1766, (2015)
13 S. Yang, X. Wang, S. Dai, X. Wang, A. S. Alshomrani, T. Hayat and B. Ahmad, Investigation of 90Sr(II) Sorption onto Graphene Oxides Studied by Macroscopic Experiments and Theoretical Calculations, J. Radioanal. Nucl. Chem., 308, 721, 2016
Page 42
14 Z. Q. Bai, Z. J. ] Li, C. Z. Wang, L. Y. Yuan, Z. R. Liu, J. Zhang, L. R. Zheng,
Y. L. Zhao, Z. F. Cha and W. Q. Shi, Interactions between Th(IV) and Graphene Oxide: Experimental and Density Functional Theoretical Investigations, RSC Adv., 4, 3340, 2014
15 S. Yu, X. Wang, X. Tan and X. Wang, Sorption of Radionuclides from Aqueous Systems onto Graphene Oxide-Based Materials: A Review, Inorg. Chem. Front., 2, 593, 2015
16 X. Deng, X. liu, T. Duan, W. Zhu, Z. Yi and W. Yao, Fabricating a Graphene Oxide-Bayberry Tannin Sponger for Effective Radionuclide Removal, Mater. Res. Express, 3, 055002, 2016
17 Y. Sun, D. Shao, C. Chen, S. Yang and X. Wang, Highly Efficient Enrichment of Radionuclides on Graphene Oxide-Supported Polyaniline, Environ. Sci. Technol., 47, 9904, 2013
18 Z. Zhao, J. Li, T. Wen, C. Shen and X. Wang, Surface Functionalization Graphene Oxide by Polydopamine for High Affinity of Radionuclides, Colloids Surf. A, 482, 258, 2015
19 F. Wang, H. Li, Q. Liu, Z. Li, R. Li, H. Zhang, L. Liu, GA Emelchenko and J Wang, A Graphene Oxide/Amidoxime Hydrogel for Enhanced Uranium Capture, Sci. Rep., 6, 19367, 2016
20 M. Lozada-Hidalgo, S. Hu, O. Marshall, A. Mishchenko, A. N. Grigorenko, R. A. W. Dryfe, B. Radha, I. V. Grigorieva, A. K. Geim, Sieving Hydrogen Isotopes Through Two-Dimensional Crystals, Science, 351, 6268, 68, 2016
21 Q. Zhang, M. Ju, L. Chen and X. C. Zeng, Differential Permeability of Proton Isotopes through Graphene and Graphene Analogue Monolayer, J. Phys. Chem. Lett., 7, 3395, (2016)
22 G. Sevigny, R. Motkuri, D. Gotthold and L. S. Fifield, Separation of Tritiated Water using Graphene Oxide Membrane, US DoE Fuel Cycle Research and Development, Pacific North West Laboratory, PNNL-24411, 2015
23 S. Chuah, Z. Pan, J. G. Sanjayan, C. M. Wang and W. H. Duan, Nano Reinforced Ccement and Concrete Composites and New Perspective from Graphene Oxide, Constr. Build. Mater., 73, 113, 2014
24 K. Gong, Z. Pan, A. Korayem, L. Qiu, D. Li, F. Collins, C. Wang, W. Duan, Reinforcing Effects of Graphene Oxide on Portland Cement Paste, J. Mater. Civ. Eng., 27 (2), A4014010, 2015
25 Z. Pan, L. He, A. H. Korayem, G. Li, J. W. Zhu, F. Collins, D. Li, W. H. Duan and M. C. Wang, Mechanical Properties and Microstructure of a Graphene Oxide-Cement Composite, Cement Concrete Comp., 58, 140, 2015
Page 43
26 A. Sedaghat, M. K. Ram, A. Zayed, R. Kamal and N. Shanahan, Investigation
of Physical Properties of Graphene-Cement Composite for Structural Applications, Open Journal of Composite Materials, 4, 12, 2014
27 NDA RWMD, Encapsulation of GLEEP Fuel at Harwell (Final stage – close out of Action Points) – Summary of Assessment Report, February 2011
28 M. A. Rafiee, J. Rafiee, Z. Wang, H. Song, Z. Z. Yu and N. Koratkar, Enhanced Mechanical Properties of Nanocomposites at Low Graphene Content, ACS Nano, 3 (12), 3884, 2009
29 T. Ramanathan, A. A. Abdala, S. Stankovich, D. A. Dikin, M. Herrera-Alonso, R. D. Piner, D. H. Adamson, H. C. Schniepp, X. Chen, R. S. Ruoff, S. T. Nguyen, I. A. Aksay, R. K. Prud’Homme, and L. C. Brinson, Functionalized Graphene Sheets for Polymer Nanocomposites, Nat. Nanotechnol., 3, 327, 2008
30 M. Fang, K. Wang, H. Lu, Y. Yang and S. Nutt, Covalent Polymer Functionalization of Graphene Nanosheets and Mechanical Properties of Composites, J. Mater. Chem., 19, 7098, 2009
31 N. Domun et al., Improving the Fracture Toughness and the Strength of Epoxy using Nanomaterials – a Review of the Current Status. Nanoscale, 7, 10294-10329 (2015)
32 M. Foxe, G. Lopez, I. Childres, R. Jalilian, A. Patil, C. Roecker, J. Boguski, I. Jovanovic and Y. P. Chen, Graphene Field-Effect Transistors on Undoped Semiconductor Substrates for Radiation Detection, IEEE Trans. Nanotechnol., 11 (3), 581, 2012
33 E. Cazalas, B. K. Sarker, M. E. Moore, I. Childres, Y. P. Chen and I. Jovanovic, Position Sensitivity of Graphene Field Effect Transistors to X-Rays, Appl. Phys. Lett., 106, 223503, 2015
34 E. X. Zhang, A. K. M. Newaz, B. Wang, S. Bhandaru, C. X. Zhang, D. M. Fleetwood, K. I. Bolotin, S. T. Pantelides, M. L. Alles, R. D. Schrimpf, S. M. Weiss, R. A. Reed and R. A. Weller, Low-Energy X-ray and Ozone-Exposure Induced Defect Formation in Graphene Materials and Devices, IEEE Trans. Nucl. Sci., 58 (6), 2961, 2011
35 F. Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake, M. I. Katsnelson and K. S. Novoselov, Detection of Individual Gas Molecules Adsorbed on Graphene, Nat. Mater., 6, 652, 2007
36 T. Wang, D. Huang, Z. Yang, S. Xu, G. He, X. Li, N. Hu, G. Yin, D. He and L. Zhang, A Review on Graphene-based Gas/Vapor Sensors with Unique Properties and Potential Applications, Nano Micro Lett., 8(2), 95, 2016
37 S.F. Ashley, Graphene Literature Review Supporting Information, NS4145-420-001, Issue 1, March 2017.
Page 44
38 A. M. Pinto, , I. C. Goncalves and F. D. Magalhães, Graphene-based
Materials Biocompatibility: A Review, Colloids and Surfaces B: Biointerfaces 111, 188– 202, 2013
39 J. Zhao, Z. Wang, J. C. White and B. Xing, Graphene in the Aquatic Environment: Adsorption, Dispersion, Toxicity and Transformation, Environ. Sci. Technol., 48, 9995−10009, 2014
40 R. Arvidsson, S. Molander and B. A. Sanden, Review of Potential Environmental and Health Risks of the Nanomaterial Graphene, Human and Ecological Risk Assessment, 19: 873–887, 2013
41 D. Finnigan and R. Thorington, Graphene: The Opportunities and Threats of Emerging Technologies, February 2016
42 A. J. Pollard, Metrology for Graphene and 2D Materials, Meas. Sci. Technol. 27, 09200, 13pp, 2016
43 K Alexandrou, A Masurkar and H Edress et. al., Improving the Radiation Hardness of Graphene Field Effect Transistors, Appl. Physics Letters, 109, 2016
44 A Ansón-Casaos, J A Puértolas, F J Pascual et. al., The Effect of Gamma-Irradiation on Few-Layered Graphene Materials, Appl. Surface Sci., 301, 264-272, 2014
45 Y Wang, Y Feng, F Mo et. al., Influence of Irradiation upon Few-Layered Graphene using Electron-Beams and Gamma-Rays, Appl. Physics Letters, 102, 2014
46 K Alexandrou, Ionizing Radiation Effects on Graphene Based Field Effects Transistors, Doctor of Philosophy Thesis, Columbia University, 2016
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Appendix A Detailed Output from the Desktop Review of Graphene research areas # Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
Research identified from The Graphene Flagship
#1 University of
Manchester
WP1 (Enabling
Research)
Task 1.2
Work Package
Leader:
Professor
Vladimir Falko
(University of
Manchester)
R.R. Nair, at al.
Science 335, 442
(2012).
R.K. Joshi, et al.
Science 343, 752
(2014).
G. Algara-Siller,
et al. Nature 519,
443-445 (2015
― Investigation of nanocapillary properties of graphene- and
hBN-based structures; development of intercalated graphene
structures. Example: graphene laminate that would filter out
>80% of salt ions from water over one pump cycle.
Manchester University have recently found that graphene-
based nanocapillaries with a size of »10 Å, made by a
bottom-up technique using graphene oxide, provide
practically no barrier for water vapour permeation and offer
remarkable properties for water filtration. The latest research
shows that water inside such graphene nanocapillaries forms
square ice at room temperature. They work to develop top-
down technologies for fabricating nanocapillaries from
graphene, hBN and other 2D materials and investigate their
properties in view of their applications in separation of gas
mixtures and desalination of water.
Desalination Yes
Page 46
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#2 Friedrich-
Schilleruniversitat
Jena
WP3 (Enabling
Materials)
Task 3.1.2
Work Package
Leader:
Professor Mar
Garcia-
Hernandez,
CSIC, Consejo
Superior de
Investigaciones
Cientificas,
P. Angelova, et
al. ACS Nano 7,
6489-6497
(2013)
― The goal of this activity is to scale-up the technology for
synthesis of graphene membranes.
Growth of membranes and their heterostructures by electron
beam crosslinking of self-assembled molecules. Structural,
electrical, optical, mechanical characterisation. Permeation
tests.
Growth and characterisation of membranes of other 2D
materials from LPE by vacuum filtering.
Patterning with nanoimprint lithography.
Potential use of advanced membranes to be used for various
nuclear decommissioning projects
Membranes Yes
#3 Friedrich-
Alexanderuniversita
et Erlangen
Nuernberg
WP3 (Enabling
Materials)
Task 3.1.6
Work Package
Leader:
Professor Mar
Garcia-
Hernandez,
(CSIC)
S. Eigler and A.
Hirsch,
Angewandte
Chemie
International
Edition 53, 7720-
7738, (2014).
― Chemical and physical modification of 2D materials for
various applications. Achieve < ppm sensitivity for graphene-
based gas sensors for H2O, O2, NH3 and NO2. Covalent
coupling of bio and organic species on graphene for
biosensors. Graphene-based devices respond to the
presence of very small amounts of gases in the ambient
atmosphere or to adsorption of molecules on its surface.
However, specificity of this response can only be achieved by
a combination of graphene sensor with functional molecular
or atomic groups. The aim of this task is to develop methods
to functionalise graphene for gas and bio applications.
Sensors Yes
#4 CNM Technologies
GmbH
WP3 (Enabling
Materials)
Task 3.2.3
Work Package
Leader:
Professor Mar
Garcia-
Hernandez,
(CSIC)
― ― Scale-up production of graphene membranes with transfer
and their incorporation in standard filtration device structures,
characterisation of their filtration properties. Device-scale
engineering, integration and quality control of membranes.
The participation of BASF is of particular note.
Membranes Yes
Page 47
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#5 Universidad de
Castilla - La
Mancha
WP4 (Health &
Environment)
Task 4.1
Work Package
Leader:
Professor
Maurizio Prato,
University of
Trieste, Italy
WP Outputs:
Wick P, 2014.
Angew Chem Int
Ed Engl. 53 (30):
7714-7718
― Preparation of graphene enriched with stable and radioactive
isotopes: Synthesis and characterisation of 14C-labelled
graphene and 13C graphene and graphene oxide,
instrumental to biodistribution routes studies. The aim of this
task is to determine the kinetics and fate of graphene via
aspiration route of exposure. It will include: 1) synthesis of
graphene from 13C-labelled methane 14C-benzene precursor
by CVD 2) in vivo administration of 14C-labelled graphene
suspensions to mice, 3) full-body radioimaging, and 4)
extraction of graphene from target organs and
characterization by high-resolution TEM.
This work is of general H&S interest. It evaluates the risks to
humans if graphene and related materials are to be used in
practical applications.
Health and
Safety/
Environment
Potentially
#6 Commissariat a
l’Energie Atomique
et Aux Energies
Alternatives (CEA)
WP4 (Health &
Environment)
Task 4.9
Work Package
Leader:
Professor
Maurizio Prato,
University of
Trieste, Italy
As (5) ― Biodistribution of inhaled radiolabelled graphene: GRM bio-
persistence beyond respiratory barriers. The aims and
relevance to the nuclear industry for this Task is detailed in
(5).
Health and
Safety/
Environment
Potentially
Page 48
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#7 TU Delft WP6 (Sensors)
Task 6.1
Work Package
Leader: Herre
van der Zant,
Technical
University of
Delft, The
Netherlands
WP Outputs:
Dolleman R. J., et
al., Nano Lett.,
16, 568 (2016)
― Sensor fabrication and functionalization. Suspended
graphene devices form the basis for four types of sensor
applications pursued within WP6: pressure, gas and mass
sensing and the translocation of DNA through nanopores.
Large arrays of suspended CVD graphene membranes
deposited on electrodes for electrical readout and actuation
will be fabricated.
Gas analysers in particular may be interesting for ND
industry. In addition, calibrated nanopores can be used in
other types of devices, e.g., for filtration.
Sensors Yes
#8 TU Delft WP6 (Sensors)
Task 6.2
Work Package
Leader: Herre
van der Zant,
Technical
University of
Delft, The
Netherlands
― ― Sensor fabrication and functionalization. Gas sensing will be
pursued using different platforms. Resistive sensors are
based on field-effect transistors functionalized by PLD or
using nanopatterning; they respond to the presence of gases
adsorbed on the surface by a measurable change in
resistance due to doping or scattering effects. In resonant
devices, graphene membranes are used as resonators and
gas detection can be established through the adsorbed mass
of the gas molecules and the accompanying change in
resonant frequency or by a change of the dynamic properties
in case nanoporous graphene is used. Optical read-out of
gases using graphene plasmonics will also be examined. A
major goal is to develop working principles for the miniature
low-power sensors of the main pollutant gases (NOx, O3, CO,
SO2, NH3). The working principles can in the future be
extended to other gases.
Sensors Yes
Page 49
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#9 TU Delft WP6 (Sensors)
Task 6.4
Work Package
Leader: Herre
van der Zant,
Technical
University of
Delft, The
Netherlands
― ― Technology and feasibility assessment of GRM sensors.
Feasibility and technology readiness assessment for
application of graphene-related materials in sensor
applications.
Sensors Yes
#10 Politecnico di
Milano
WP7 (Electronic
Devices)
Task 7.1
Work Package
Leader: Dr
Daniel
Neumaier,
AMO GmbH,
Germany
― ― This task is dedicated to the development of process
technology for the fabrication of graphene and transition-
metal-dichalcogenide (TMD) field-effect transistors (FETs)
and passive multilayer devices. Ultrathin stable gate-stacks
will be developed and optimized for graphene FETs (GFETs)
fabricated from CVD-grown and hydrogen-intercalated
epitaxial graphene and optimized for GFETs fabricated on
quartz, high resistivity Si, SiO2 and SiC.
This work is relevant to the development of GFET radiation
sensors.
Radiation
Detectors
Yes
#11 TU-Wien WP8 (Photonics &
Optoelectronics)
Task 8.1
Work Package
Leader:
Professor Frank
Koppens,
ICFO, Spain
― ― Photo-detectors for visible, near-IR and shortwave IR,
including waveguide-integrated PDs for the silicon-on-
insulator platform, Ultra-sensitive PDs for low-intensity or
single-photon detection, flexible photodetectors. The
relevance of this work is in the potential to develop better,
more sensitive and compact heat-sensitive detectors and
cameras, or THz for non-destructive examination and testing.
Radiation
Detectors
Yes
#12 Fondazione Bruno
Kessler
WP8 (Photonics &
Optoelectronics)
Task 8.6
Work Package
Leader: Frank
Koppens,
ICFO, Spain
― ― Long-wavelength photo-detectors, such as high-response-
speed THz field effect transistors, mid-IR detectors with pn-
junctions and photodiodes. The aims and relevance to the
nuclear industry for this Task is detailed in (11).
Sensors;
Advanced
Electronics
Yes
Page 50
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#13 ST Microelectronics
SRL
WP9 (Flexible
Electronics)
Task 9.3
Work Package
Leader: Henrik
Sandberg, VTT
Technical
Research
Center of
Finland Ltd.,
Finland
― ― Flexible Sensing Modules including logic and, in some case,
wireless connectivity, suitable for applications in ‘Wearables’
and ‘Distributed Sensors Networks’. In summary, this work
involves developing miniaturised sensors and associated
wireless electronics.
Sensors;
Advanced
Electronics
Potentially
#14 Universite des
Sciences et
Technologies de
Lille
WP9 (Flexible
Electronics)
Task 9.4
Work Package
Leader: Henrik
Sandberg, VTT
Technical
Research
Center of
Finland Ltd.,
Finland
― ― Flexible Radio Modules: flexible connectivity modules,
identifying possible key applications (wearables, etc.). In
summary, this work involves developing miniaturised sensors
and associated wireless electronics.
Sensors;
Advanced
Electronics
Potentially
#15 Flexenable Limited WP9 (Flexible
Electronics)
Task 9.5
Work Package
Leader: Henrik
Sandberg, VTT
Technical
Research
Center of
Finland Ltd.,
Finland
― ― Flexible user interface modules. In summary, this work
involves developing miniaturised sensors and associated
wireless electronics.
Sensors;
Advanced
Electronics
Potentially
Page 51
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#16 Nokia R&D WP10 (Wafer-Scale
System Integration)
Task 10.4
Work Package
Leader:
Professor
Marco
Romagnoli,
CNIT, Italy
― ― Flexible electronics: Large-scale monolithic integration of
GRM-based circuits, large-scale heterogeneous integration of
multiple GRM-based components on flexible. In summary,
this work involves developing miniaturised sensors and
associated electronics with wireless.
Sensors;
Advanced
Electronics
Potentially
#17 Sabanci University WP11 (Energy
Generation)
Task 11.2
Work Package
Leader: Dr
Gerard Gebel,
CEA French
Alternative
Energies and
Atomic Energy
Commission,
France.
WP Outputs:
Quesnel E., et al.,
2D Mater. 2,
030204 (2015)
Konios D., et al.,
J. Mater. Chem.
A, 4, 1612 (2016)
Casalucci S., et
al., Nanoscale
(2016)
― Fuel Cells: very low Pt content electrodes and hierarchical
nanostructured electrocatalysts: towards Pt-free electrodes.
Excess heat generated by the nuclear power stations can be
directly converted into electric power using fuel cells.
Lightweight portable autonomous power sources will be
important in wireless sensor networks and robots.
Fuel Cells Potentially
#18 Tor Vergata WP11 (Energy
Generation)
Task 11.3
Work Package
Leader: Dr
Gerard Gebel,
CEA French
Alternative
Energies and
Atomic Energy
Commission,
France.
As (17) ― Technology Up-scaling: PV and fuel cell demonstrators. The
aims and relevance to the nuclear industry for this Task is
detailed in (17).
Fuel Cells Potentially
Page 52
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#19 Thales SA WP12 (Energy
Storage)
Task 12.1
Work Package
Leader: Dr
Vittorio
Pellegrini, IIT
Graphene
Labs, Istituto
Italiano di
Tecnologia,
Italy.
WP Outputs:
Liu T. et al.,
Science, 350,
6260, 530 (2015)
― Supercapacitors: high-surface area and pseudocapacitive
materials, graphene-based electrodes, EDLC and hybrid
devices, flexible supercapacitors, spray-deposited
supercapacitors. Lightweight portable autonomous power
sources will be important in wireless sensor networks and
robots. Gas storage applications of 3D porous graphene
networks are of particular interest for nuclear
decommissioning and energy generation industries
(hydrogen storage).
Gas Storage Potentially
#20 University of
Cambridge
WP12 (Energy
Storage)
Task 12.2
Work Package
Leader: Dr
Vittorio
Pellegrini, IIT
Graphene
Labs, Istituto
Italiano di
Tecnologia,
Italy.
As (19) ― Batteries: anodes and cathodes for Li-ion/Na-ion batteries,
conformable and transparent batteries. The aims and
relevance to the nuclear industry for this Task is detailed in
(19).
Gas Storage Potentially
#21 Umea Universitet WP12 (Energy
Storage)
Task 12.3
Work Package
Leader: Dr
Vittorio
Pellegrini, IIT
Graphene
Labs, Istituto
Italiano di
Tecnologia,
Italy.
As (19) ― Gas storage: porous 3D architectures with high surface area,
adsorption optimisation. The aims and relevance to the
nuclear industry for this Task is detailed in (19).
Gas Storage Potentially
Page 53
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#22 TU Dresden WP13 (Functional
Foams and
Coatings)
Task 13.1
Work Package
Leader:
Professor
Xinliang Feng,
TU Dresden,
Germany
― ― Functionalization and processing of nanocomposites for
integration into functional composites, templated synthesis of
2D composites. The porous structures with well-developed
surface areas may find applications in mopping spillage,
filtration, chromatographic columns, gas storage, etc. In
addition, graphene and related materials can be used as
impermeable barrier coatings for metals and polymers, as
well as functional coatings for catalysis.
Gas Storage Yes
#23 TU Dresden WP13 (Functional
Foams and
Coatings)
Task 13.2
Work Package
Leader:
Professor
Xinliang Feng,
TU Dresden,
Germany
― ― Applications in foams and membranes: G/GRM and 2D-
nanocomposite-based porous 3D structures for energy
applications, light-weight thermally insulating and flame-
retardant materials, functionalised porous structures. The
aims and relevance to the nuclear industry for this Task is
detailed in (22).
Membranes Yes
#24 TU Dresden WP13 (Functional
Foams and
Coatings)
Task 13.3
Work Package
Leader:
Professor
Xinliang Feng,
TU Dresden,
Germany
― ― Coatings for electronics, energy storage and conversion,
protection, photocatalysis, electrodes for desalination, EMI
shielding. The aims and relevance to the nuclear industry for
this Task is detailed in (22).
Advanced
Coatings
Yes
#25 TU Dresden WP13 (Functional
Foams and
Coatings)
Task 13.4
Work Package
Leader:
Professor
Xinliang Feng,
TU Dresden,
Germany
― ― Characterization of nanocomposites and membranes. The
aims and relevance to the nuclear industry for this Task is
detailed in (22).
Membranes Yes
Page 54
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#26 National Research
Council, Italy (CNR)
WP14 (Polymer
Composites)
Task 14.1
Work Package
Leader: Dr
Vincenzo
Palermo, CNR
National
Research
Council, Italy
Kawai S., et al.,
Science, 351,
6276, 957 (2016)
― Composites processing and benchmarking, matrix interface
control. The aim is to translate the exceptional properties of
graphene from the nanoscale up to useful macroscopic
materials, in particular bulk composites based on graphene
related materials (GRM) and polymers. Strengthened and
functionalised (in terms of their thermal, electrical and other
properties) composites can find wide applications as
engineering materials including nuclear industry.
Advanced
Materials
Potentially
#27 Manchester
University
WP14 (Polymer
Composites)
Task 14.2
Work Package
Leader: Dr
Vincenzo
Palermo, CNR,
Italy
Kawai S., et al.,
Science, 351,
6276, 957 (2016)
― GRM-polymer composites with enhanced electrical charge
percolation properties for EMI shielding and stealth coatings,
high-power generation, transformation and distribution. The
aims and relevance to the nuclear industry for this Task is
detailed in (26).
Advanced
Materials
Potentially
#28 Foundation for
Research and
Technology Hellas
WP14 (Polymer
Composites)
Task 14.3
Work Package
Leader: Dr
Vincenzo
Palermo, CNR,
Italy
― ― GRM-polymer composites with enhanced mechanical,
thermal and chemical stability for gas barriers, smart barriers
for heat pipes, applications in aeronautics and automotive
industry, such as for reduced flammability. The aims and
relevance to the nuclear industry for this Task is detailed in
(26).
Advanced
Materials
Yes
#29 Fondazione Bruno
Kessler
WP14 (Polymer
Composites)
Task 14.4
Work Package
Leader: Dr
Vincenzo
Palermo, CNR,
Italy
― ― Modelling of GRM-polymer composites. The aims and
relevance to the nuclear industry for this Task is detailed in
(26).
Advanced
Materials
Yes
#30 Avanzare
Innovacion
Tecnologica SL
WP15 (Production)
Task 15.3
Work Package
Leader: Dr Ken
Teo, Aixtron
Ltd., United
Kingdom
― ― The overall aim of the WP is to achieve economically viable
volumes of graphene and GRM production, while maintaining
the exceptional properties of these materials.
Advanced
Manufacture
Yes
Page 55
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#31 Universite de
Montpellier
WP19 (Research
Management)
Task 19.4
Work Package
Leader: Dr
Katarina
Boustedt,
Chalmers
University of
Technology,
Sweden
― ― The relevance of these tasks is that the standards and
reliable material, device and system validation instils
confidence in the quality and performance of the novel
technologies. Especially important for the nuclear industry,
where reliability is paramount.
Standards Yes
#32 Fraunhofer WP19 (Research
Management)
Task 19.5
Work Package
Leader: Dr
Katarina
Boustedt,
Chalmers
University of
Technology,
Sweden
― ― Critical assessment of the state of the art and roadmapping of
graphene/GRM research and industry.
Technology
Policy
Yes
US DOE Funded Research Projects (currently funded in 2016): 68. Data taken from Abstract keyword search “graphene” from the US DOE Portfolio Analysis and Management System.
#33 Brown University Understanding and
controlling
toughening
mechanisms in
ceramic
nanocomposites
Brian Sheldon Award No:
DE-SC0005242
2016 Work has focussed on using carbon nano-tubes to strengthen
ceramics. Current work looks to expand this with graphene
and reduced graphene oxide.
Advanced
Materials
Yes
#34 Central Michigan
University
Element specific
atomic arrangement
of nanosized
catalysts in as
prepared and active
state
Valeri Petkov Award No:
DE-SC0006877
2016 Work focusses on nanocatalysts. Particular emphasis on the
use of these in Li-batteries but also for the removal of
pollutants such as CO.
Energy/
Energy
Storage
Potentially
Page 56
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#35 Columbia University Catalytic growth of
molecular-scale
wiring
Colin Nuckolls Award No:
DE-FG02-
01ER15264
2016 Research focusses on fabricating catalysts out of low
dimensional materials. Potential overlap with novel catalysts
for use in nuclear waste management.
Advanced
Manufacture/
Fabrication
Yes
#36 Massachusetts
Institute of
Technology
Development of
scalable
manufacturing
process for high-
selectivity single-
layer nanoporous
graphene
membranes
Sean O’Hern
(as part of
GRoWater Inc.)
Award No:
DE-SC0015175
2016 Research focussed on fabricating nanoporous graphene
membranes. Particular emphasis is placed on the use of
these materials in desalination, gas separation and organic
solvents. Significantly likely that there could be overlap with
nuclear waste management.
Membranes Yes
#37 Technology
Assessment &
Transfer Inc.
Graphene reinforced
glassy carbon
particle beam
windows
Jeffery Kutsch Award No:
DE-SC0015917
2016 Use of graphene for beam windows used in particle
accelerators. Potential overlap with nuclear glasses.
Advanced
Materials
Potentially
#38 Temple University Center for the
computational design
of functional layered
materials
John Perdew Award No:
DE-SC0012575
2016 Though mainly centred on computational research. Research
focusses on (but not limited to) graphene-based catalysts. Of
potential interest if catalysis research is in scope.
Catalysis Potentially
#39 Texas A&M
University
Radiation response
of low dimensional
carbon systems
Lin Shao Award No:
DE-SC0006725
2016 Work is focussed on looking at radiation damage of various
low-dimensional materials including graphene. This work
would have particular interest where low-dimensional
materials are used in nuclear waste management.
Radiation
Tolerance
Yes
Page 57
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#40 University of Notre
Dame
Radiation and
photochemistry in
the condensed
phase and at
interfaces
Ian Carmichael Award No:
DE-FC02-
04ER15533
2016 Work centres on radiation chemistry. The laboratory has a
long-standing research effort in nuclear chemistry. This
research centres on solar cell and future energy technology
development. Whilst solar photochemistry is not directly
relevant to the nuclear industry, their characterisation at this
facility might be in scope,
Energy/
Energy
Storage;
Radiation
Tolerance
Potentially
#41 Virginia
Commonwealth
University
Elucidation of
hydride interaction
mechanisms with
carbon
nanostructures and
the formation of
novel
nanocomposites
Puru Jena Award No:
DE-SC0007033
2016 Research on the using nanomaterials in hydrogen cells and
hydrogen storage. Potential overlap with storing/trapping
materials.
Energy/
Energy
Storage
Potentially
#42 William Marsh Rice
University
Understanding and
controlling
toughening
mechanisms in
ceramic
nanocomposites
Jun Lou Award No:
DE-SC0010688
2016 Work focusses on nanocatalysts. Particular emphasis on the
use of these in Li-batteries but also for the removal of
pollutants such as CO.
Energy/
Energy
Storage
Yes
Page 58
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
NSF Funded Research Projects (currently funded in 2016): 346. Data taken from Abstract keyword search “graphene” from the NSF Awards website
#43 Auburn University GOALI/
Collaborative
Research: Improving
the performance of
electrical connectors
using extremely thin
sheets of graphene
sandwiched between
metal layers
Robert Jackson Award No:
1362126
2016 Research focusses on developing corrosion resistant
electrical connectors. The work on the corrosion processes
and characterisation may overlap with nuclear research.
Advanced
Electronics
Potentially
#44 Case Western
Reserve University
CAREER:
Asymmetric
functionalization of 2-
d nanomaterials for
tailored assemblies
Emily Pentzer Award No:
1551943
2016 Research focusses on Janus nanosheets that have the
potential to be used in advanced coatings. Such coatings
may exhibit properties that could be used in treating nuclear
waste materials.
Advanced
Coatings
Yes
#45 City University of
New York
COLLABORATIVE
RESEARCH: Nano-
engineered MOF-
graphene materials:
new perspectives for
reactive adsorption
and catalysis
Teresa Bandorz Award No:
1133112
2016 Research focusses on developing of advanced absorbents
for removing toxic gases (ammonia, hydrogen sulphide) that
could possibly be applicable to the nuclear industry.
Adsorbents Yes
#46 College of William
and Mary
DMREF:
Collaborative
Research: Polymeric
composites and
foams based on two
dimensional
surfactants
Hannes
Schneipp
Award No:
1534428
2016 Research focusses on developing graphene production that
could potentially be used to develop advanced polymers.
Such polymers may exhibit properties that could be used in
treating nuclear waste materials.
Advanced
Materials
Yes
Page 59
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#47 Columbia University GOALI/Collaborative
Research: Improving
the performance of
electrical connectors
using extremely thin
sheets of graphene
sandwiched between
metal layers
Elon Terrell Award No:
1363093
2016 Research focusses on developing corrosion resistant
electrical connectors. The work on the corrosion processes
and characterisation may overlap with nuclear research.
Advanced
Electronics
Potentially
#48 Dartmouth College DNP-enhanced
NMR surface
characterization
Chandrasekhar
Ramanathan
Award No:
1410504
2016 Research focusses on studying surface interactions, with the
potential to use graphene in advanced catalysts. Such
surface interactions could form the bases of novel sensors
that could be used in the nuclear industry.
Catalysis Potentially
#49 Graphene Frontiers
LLC
SBIR Phase II: Roll-
to-roll production of
uniform graphene
films at atmospheric
pressure and low
temperature
Bruce Willner Award No:
1330991
2016 Research focusses on the development of graphene
fabrication. The products developed can potentially have
further use in novel imaging technologies that can be used to
assess irradiated nuclear material.
Advanced
Manufacture/
Fabrication
Potentially
#50 Kansas State
University
Investigating the
structure and thermal
damage resistance
of molecular
precursor derived
ceramics for high
power laser
radiometry
Gurpreet Singh Award No:
1335862
2016 Research focusses on developing advanced ceramic
materials that are further resistant to heat damage which may
ultimate be applicable to advanced ceramics for use in the
nuclear industry.
Advanced
Materials
Yes
Page 60
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#51 Massacheusetts
Institute of
Technology
I-Corps: Application
Development for
graphene oxide
nanofiltration
membranes
Jeffrey
Grossman
Award No:
1649058
2016 Research focusses on developing advanced membranes.
Such membranes could be used in improved filters in
wastewater treatment that could be used to treat nuclear
wastes.
Membranes Yes
#52 Nanomaterial
Innovation Ltd,
SBIR Phase II:
Carbide bonded
graphene coating for
enhanced glass
molding
Jianfeng Yu Award No:
1456921
2016 Research considers advanced coatings for plastics to
improve their optical properties. Such coatings may also
possibly have use in the nuclear industry.
Advanced
Coatings
Potentially
#53 Rochester Institute
of Tech.
Ultra high boiling
performance on
nano/microstructured
surfaces through
electrodeposition of
copper and
graphene
Satish
Kandlikar
Award No:
1335927
2016 Research considers the study of heat transfer between
graphene and copper that may potentially develop materials
with improved heat transfer.
Heat Transfer Potentially
#54 State University of
New York at
Binghamton
Collaborative
Research:
Experimental and
computational
nanomechanics of
the load transfer
mechanisms at the
graphene polymer
interface
Changhong Ke Award No:
1537333
2016 Research considers the use of polymer nanocomposites,
especially graphene, in advanced polymers and looks to
study the graphene-polymer interface. Such advanced
polymers may potentially be used to encapsulating nuclear
waste.
Advanced
Materials
Potentially
Page 61
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#55 University of
Connecticut
DMREF:
Collaborative
Research: Polymeric
composites and
foams based on two
dimensional
surfactants
Douglas
Adamson
Award No:
1535412
2016 Research focusses on developing graphene production that
could potentially be used to develop advanced polymers.
Such polymers may exhibit properties that could be used in
treating nuclear waste materials.
Advanced
Materials
Yes
#56 University of
Houston
CAREER:
Toxicology of
graphene-based
nanomaterials: A
molecular
biotechnology
approach
Deborah
Rodrigues
Award No:
1150255
2016 Research looks at graphene-based nanomaterials and their
impact on microbial populations used in wastewater
treatment. Such research may overlap with the interactions
between water, microbes, and graphene-based wastes in a
repository environment.
Water
Treatment
Potentially
#57 University of Illinois
at Urbana-
Champaign
Collaborative
Research:
Experimental and
computational
nanomechanics of
the load transfer
mechanisms at the
graphene polymer
interface
Huck Beng
Chew
Award No:
1538162
2016 Research considers the use of polymer nanocomposites,
especially graphene, in advanced polymers and looks to
study the graphene-polymer interface. Such advanced
polymers may potentially be used to encapsulating nuclear
waste.
Advanced
Materials
Potentially
#58 University of Illinois
at Urbana-
Champaign
Imaging the surface
dynamics of glasses
and photoexcited
molecules
Martin Gruebele Award No:
1307002
2016 Research considers various advanced materials to probe the
underlying theories on glasses. Developments in novel
glasses could be used in the nuclear industry.
Advanced
Materials
Potentially
Page 62
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#59 University of
Massachusetts
Amherst
Collaborative
Research: Self-
exfoliation as
promising route to
novel
nanocomposite
processing
H. Henning
Winter
Award No:
1334460
2016 Research considers the use of graphene and clays to form
advanced polymer matrices. Such advanced polymers may
have better thermal characteristics that could potentially
impact on novel encapsulants.
Advanced
Materials
Potentially
#60 University of
Massachusetts
Dartmouth
Mechanics of multi-
functional
biocomposites
Vijaya
Chalivendra
Award No:
1563040
2016 Research considers the use of applying graphene-based
materials to natural fibres. This could potentially be used in
novel construction materials.
Advanced
Materials
Potentially
#61 University of North
Carolina at
Charlotte
Environment
assisted cracking of
graphene
Alireza Tabarrei Award No:
1563224
2016 Research focusses on the potential for graphene to undergo
stress-corrosion-cracking and to further understand the
material property of graphene. Results of this research could
indicate the viability of graphene-based materials in the
nuclear industry.
Corrosion Yes
#62 University of Toledo I-Corps Teams:
Customer discovery
activity for
microelectromechani
cal systems based
gas sensors
Ahalapitiya
Jayatissa
Award No:
1644894
2016 Research outlines the development of novel gas-detecting
sensors. Such sensors may potentially be useful in novel
detectors that are relevant to the nuclear industry.
Sensors Potentially
Page 63
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#63 Washington
University
CAREER:
Development and
application of
crumpled graphene
oxide-based
nanocomposites as
a platform material
for advanced water
treatment
John Fortner Award No:
1454656
2016 Research includes the use of graphene in novel water
treatment facilities. Such techniques may be applicable to
wastewater treatment in the nuclear industry.
Water
Treatment
Potentially
Research Outputs and Patents from DOE funded research: 1656. Data taken from Abstract and Title keyword search “Graphene” from the OSTI website
#64 Ames Lab. (AMES),
Ames, IA (United
States)
Adsorption and
diffusion of Ru
adatoms on
Ru(0001)-supported
graphene: Large-
scale first-principles
calculations
Yong Han Journal Article
DOI:10.1063/1.49
34349
2015 Theoretical condensed matter. Normally out-of-scope;
however, this research considers the adsorption processes of
Ru atoms which may potentially have cross-over for the
nuclear industry.
Fundamental
Physics
Potentially
#65 Argonne National
Lab. (ANL),
Argonne, IL (United
States)
Nanocarbon
synthesis by high-
temperature
oxidation of
nanoparticles
Ken-ichi
Nomura
Journal Article
10.1038/srep241
09
2016 Research focusses on potential use of silicon-carbide
nanoparticles. Tenuously of interest due to its potential heat
resistance.
Advanced
Materials
Potentially
#66 Argonne National
Laboratory (ANL),
Argonne, IL (United
States)
Nanoparticles for
heat transfer and
thermal energy
storage
Dileep Singh Patent Ref:
9,080,089
2015 Patent considers how nanoparticles can be used for heat
transfer processes and storing thermal energy.
Advanced
Materials
Yes
Page 64
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#67 INL (Idaho National
Laboratory (United
States))
Charged particle
detectors with active
detector surface for
partial energy
deposition of the
charged particles
and related methods
David W. Gerts Patent Ref:
8,378,308
2013 Patent discloses a radiation detector that uses graphene one
or more layers at the active detector surface.
Radiation
Detectors
Yes
#68 Ernest Orlando
Lawrence Berkeley
National Laboratory,
Berkeley, CA (US)
Writable graphene:
Breaking sp2 bonds
with soft X-rays
S. Zhou Journal Article
LBNL-3487E
2010 Article considers the stability of graphene samples to soft x-
rays. Could potentially overlap understanding the radiation
hardness of graphene-based materials.
Advanced
Materials
Potentially
#69 Lawrence Berkeley
National Lab.
(LBNL), Berkeley,
CA (United States)
Toughness and
strength of
nanocrystalline
graphene
Ashivini
Shekhawat
Journal Article
DOI:
10.1038/ncomms
10546
2016 Work considers testing the mechanical strength of graphene,
which may underpin its viability for specific applications
Advanced
Materials
Potentially
#70 Lawrence Berkeley
National Lab.
(LBNL), Berkeley,
CA (United States)
Graphene
oxide/metal
nanocrystal
multilaminates as the
atomic limit for safe
and selective
hydrogen storage
Eun Seon Cho Journal Article
DOI:
10.1038/ncomms
10804
2016 Though considered here for energy storage, the potential use
of graphene to trap hydrogen may be of interest in the field of
nuclear decommissioning.
Energy/
Energy
Storage
Yes
#71 Lawrence
Livermore National
Laboratory (LLNL),
Livermore, CA
Water confined in
nanotubes and
between graphene
sheets: A first
principle study
G. Cicero Journal Article
DOI:
10.1021/ja07441
8+
2008 Though this theoretical work is in the field of nanotechnology
and nanobiology, the study focusses on the confinement of
water.
Fundamental
Physics
Yes
Page 65
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#72 Lawrence
Livermore National
Laboratory (LLNL),
Livermore, CA
(United States)
Highly compressible
3D periodic
graphene aerogel
microlattices
Cheng Zhu Journal Article
DOI:
10.1038/ncomms
7962
2015 Work on the development of graphene-based aerogel which
may potentially be used as a thermal insulating material.
Advanced
Materials
Potentially
#73 Lawrence
Livermore National
Laboratory (LLNL),
Livermore, CA
(United States)
Graphene aerogels Peter J
Pauzauskie
Patent 2015 Work on the development of graphene-based aerogel which
may potentially be used as a thermal insulating material.
Advanced
Materials
Potentially
#74 Los Alamos
National Laboratory
(LANL)
Carbon
nanomaterials in
silica aerogel
matrices
Christopher E
Hamilton
Journal Article
DOI:
10.1557/PROC-
1258-R05-11
2010 Work on the development of graphene-based aerogel which
may potentially be used as a thermal insulating material.
Advanced
Materials
Potentially
#75 Los Alamos
National Laboratory
(LANL), Los
Alamos, NM (United
States)
Electrocatalytic
interface based on
novel carbon
nanomaterials for
advanced
electrochemical
sensors
Ming Zhou Journal Article
DOI:
10.1002/cctc.201
500198
2015 Development of advanced electrochemical sensors that may
potentially have applications for the nuclear industry.
Sensors Potentially
#76 National Energy
Technology Lab.,
Pittsburgh, PA (US);
National Energy
Technology Lab.,
Morgantown, WV
(US)
Optimization of char
for NOx removal
J. Phillips Technical Report
DOI:
10.2172/769859
1999 Studies surrounding the gas treatment using activated carbon
containing NOx, Could have potential overlap on the
treatment of gaseous nitrogen-based wastes
Gas
Separation
Yes
Page 66
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#77 Oak Ridge National
Laboratory
DOE Hydrogen
Sorption Center of
Excellence:
Synthesis and
processing of single-
walled carbon
nanohorns for
hydrogen storage
and catalyst supports
David B.
Geohegan
Technical Report
DOI:
10.2172/1024604
2011 Development of novel carbon structures with the potential use
in hydrogen cells, which may have cross-over in capturing
tritium
Advanced
Materials
Yes
#78 Oak Ridge National
Laboratory (ORNL),
Oak Ridge, TN
(United States)
Selectivity trend of
gas separation
through nanoporous
graphene
Hongjun Liu Journal Article
DOI:
10.1016/j.jssc.20
14.01.030
2014 This work covers theoretical molecular dynamics calculations
to underpin how gas separation occurs in graphene. Results
of this study impact on the gas separation uses for graphene.
Fundamental
Physics
Yes
#79 Oak Ridge National
Laboratory (ORNL),
Oak Ridge, TN
(United States)
Translational
diffusion of water
inside hydrophobic
carbon micropores
studied by neutron
spectroscopy and
molecular dynamics
simulation
S.O. Diallo Journal Article
DOI:
10.1103/PhysRe
vE.91.022124
2015 Experimental work that considers external factors that affect
the diffusion of water. Potential overlap into novel membranes
Fundamental
Physics
Potentially
#80 Oak Ridge National
Laboratory (ORNL),
Oak Ridge, TN
(United States).
Center for
Nanophase
Materials Sciences
(CNMS)
Water desalination
using nanoporous
single-layer
graphene with
tunable pore size
Sumedh P.
Surwade
Journal Article
DOI:
10.1038/nnano.2
015.37
2015 Details the development of advanced graphene-based
membranes which although planned for desalination may be
used in treating nuclear waste water.
Membranes Yes
Page 67
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#81 Pacific Northwest
National Laboratory
(PNNL), Richland,
WA (United States)
Separation of tritiated
water using
graphene oxide
membrane
Gary J. Sevigny Technical Report
DOI:
10.2172/1222908
2015 Details the development of advanced graphene-based
membranes for the use of isolation tritiated waste.
Membranes Yes
#82 Sandia National
Laboratories (SNL-
NM), Albuquerque,
NM (United States)
Exploring graphene
field effect transistor
devices to improve
spectral resolution of
semiconductor
radiation detectors
Richard Karl
Harrison
Technical Report
DOI:
10.2172/1200672
2013 Development of advanced graphene-based electronics in
developing novel radiation detector systems.
Radiation
Detectors
Yes
#83 Sandia National
Laboratories (SNL-
NM), Albuquerque,
NM (United States)
New radiological
material detection
technologies for
nuclear forensics:
Remote optical
imaging and
graphene-based
sensors
Richard Karl
Harrison
Technical Report
DOI:10.2172/121
4453
2015 Development of advanced graphene-based radiation
detectors.
Radiation
Detectors
Yes
#84 Sandia National
Laboratories (SNL-
NM), Albuquerque,
NM (United States)
Gas permeability of
graphene oxide
membranes
Laura Butler
Biedermann
Conference
SAND2012-
10172C
2012 No abstract provided, gas permeability though the potential
for advanced graphene-based membranes to be used in the
nuclear industry.
Membranes Yes
Page 68
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
Wider International Literature Review
Graphene Radionuclide Removal – Broad Area: Graphene Oxide for Radionuclide Removal and/or Heavy Metal Sorption
#85 Chinese Academy
of Science
Highly Efficient
Enrichment of
Radionuclides on
GO Supported
Polyaniline
Xiangke Wang Environmental
Science &
Technology
2013 Graphene oxide-supported polyaniline (PANI@GO)
composites for the sorption of U(VI), Eu(III), Sr(II), and Cs(I)
from aqueous solutions as a function of pH . The maximum
sorption capacities of U(VI), Eu(III), Sr(II), and Cs(I) on the
PANI@GO composites at pH 3.0 and T = 298 K calculated
from the Langmuir model were 1.03, 1.65, 1.68, and 1.39
mmol·g−1, respectively.
Water
Treatment;
Radionuclide
Remediation
Yes
#86 Rice University,
USA
Lomonosov
Moscow State
University, Russia
Graphene oxide for
effective radionuclide
removal
Prof. James
Tour
PCCP 2013 Graphene oxide (GO) for rapid removal of some of the most
toxic and
Radioactive long-lived human-made radionuclides from
contaminated water, even from acidic solutions.
The interaction of GO with actinides including Am(III), Th(IV),
Pu(IV), Np(V), U(VI) and typical fission products Sr(II), Eu(III)
and Tc(VII) were studied, along with their sorption kinetics.
Cation/GO coagulation occurs with the formation of
nanoparticle aggregates of GO sheets, facilitating their
removal.
GO is far more effective in removal of transuranium elements from simulated nuclear waste solutions than other routinely used sorbents such as bentonite clays and activated carbon.
Water
Treatment;
Radionuclide
Remediation
Yes
Page 69
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#87 The University of
Manchester
Selective removal of
technetium from
water using
graphene oxide
membranes
Christopher
Williams and
Paola Carbone
Environmental
Science &
Technology
2016 Molecular dynamic simulations on the ability for graphene
oxide membranes to remove 99Tc present in the form of
pertechnetate (TcO4-) from water
Results indicate high selectivity for the ion
Water
Treatment;
Radionuclide
Remediation
Yes
Graphene Radiation/Irradiation Tolerance, Irradiation Damage, Coatings
#88 Nanjing University,
Jiangsu Key Laboratory of Nuclear Energy Equipment Materials Engineering, China
Radiation damage
resistance and
interface stability of
copper-graphene
nanolayered
composite
Da Chen Journal of
Nuclear Materials
(note: only three
papers relating to
graphene have
been published in
this journal)
2015 The radiation damage resistance and interface stability of
copper–graphene nanolayered composite are studied by
atomistic simulations. Results show that the number of
surviving point defects in bulk region is always less than that
of pure copper at 100 K, when the range of initial
distance d between a primary knock-on atom (PKA) with
3 keV and copper–graphene interface is less than 4 nm. The
above phenomenon also occurs at 300, 500, and 700 K
when d is ∼15.4 Å, thereby implying that the composite
resulting from copper–graphene interfaces exhibits excellent
ability to resist radiation damage. A higher PKA energy
corresponds to worse radiation damage of graphene in the
composite. The damage may impair interface stability and
eventually weaken the radiation damage resistance of the
composite.
Advanced
Materials;
Advanced
Coatings
Potentially
Page 70
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#89 University of
Zaragoza
Centro Universitaro
de la Defensa de
Zaragoza,
Spain
The effect of
gamma-irradiation on
few/layered
graphene
M. T. Martinez Journal of
Applied Surface
Science
2014 Investigating γ-irradiation on the structure and composition of
chemically synthesized few-layered graphene materials.
Fully oxidized graphene oxide and graphene nanoribbons, as
well as their respective chemically post-reduced forms, were
treated under γ-irradiation in an air-sealed environment.
Three different irradiation doses of 60, 90 and 150 kGy were
applied.
The XRD patterns were not affected by γ-irradiation, and
small changes were observed in the FTIR and TGA results.
However, significant modifications were detected by Raman
spectroscopy and XPS, particularly in the Raman G/D band
intensity ratios and in the C 1s XPS profiles. Comparatively,
the changes in Raman and XPS spectra after γ-irradiation
were even greater than those occurring during the chemical
reduction of graphene oxides.
Results indicate that the graphene carbon lattice was strongly
affected by γ-irradiation, but the materials experienced small
variations in their oxygen content.
Advanced
Materials
Potentially
#90 Inter University
Accelerator Centre,
India
Radiation stability of
graphene under
extreme conditions
D. K. Avasthi Applied Physics
Letters
2014 Radiation stability of graphene under extreme conditions of
high energy density generated by 150 MeV Au ion irradiation.
Results indicate that graphene is radiation resistant for
irradiation at 1014ions/cm2 of 150 MeV Au ions.
Annealing effects are observed at lower fluences whereas
defect production occurs at higher fluences: however
crystallinity is still retained.
Radiation
Tolerance
Potentially
Page 71
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#91 Kodak Technology
Center, USA
Characterisation of
X-ray irradiated
graphene oxide
coatings using X-ray
diffraction, X-ray
photoelectron
spectroscopy and
AFM
D. Majumdar https://www.camb
ridge.org/core/ser
vices/aop-
cambridge-
core/content/view
/S088571561300
0109
2013 GO coatings are reduced to RGO upon exposure to high
energy X-rays.
RGO coating is conductivity and could be used as a cheap
coating sensor to measure radiation leaks.
Advanced
Coatings;
Sensors
Potentially
#92 University of
Manchester
Control of Radiation
Damage in MoS2 by
Graphene
Encapsulation
K. Novoselov ACS Nano 2013 Investigation into effect of 60 KeV beam on bare monolayer
MoS2 with and without graphene sandwich layers
Ionization effects can be prevented on MoS2 when
encapsulated between graphene monolayers
Advanced
Coatings
Potentially
Graphene-based Composites
#93 Korea Advanced
Institute of Science
and Technology,
Korea
Radiation Resistant
Vanadium-Graphene
Nanolayered
Composite
Seung Min Han Scientific Reports 2016 Investigation of the effect of radiation tolerance on V-
graphene nanolayers
Radiation induced hardening, evaluated via nanopillar
compressions before and after He+ irradiation, is significantly
reduced with the inclusion of graphene layers; the flow
stresses of V-graphene nanolayers with 110 nm repeat layer
spacing showed an increase of 25% while pure V showed an
increase of 88% after He+ dosage of 13.5 dpa.
Impermeability of He gas through the graphene resulted in
suppression of He bubble agglomerations that in turn
reduced embrittlement. In-situ SEM compression also
showed the ability of graphene to hinder crack propagation
that suppressed the failure.
Advanced
Materials;
Radiation
Tolerance
Potentially
Page 72
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#94 East China
University of
Science and
Technology
Fabrication of
Natural
Rubber/Chemically
Reduced Graphene
Oxide
Nanocomposites and
Nuclear Radiation
Resistant Behaviour
Luan Weiling Chemical Journal
of Chinese
Universities
2016 Investigation into the effect of γ-radiation on natural
rubber/chemically reduced graphene oxide.
After a dose of 200 kGy, the tensile strength of the pure
rubbers are decreased by 75 % compared to 56 % for the
graphene/rubber composite.
Advanced
Materials;
Radiation
Tolerance
Potentially
#95 Nanjing University
of Aeronautics and
Astronautics, China
Functionalized
graphene serving as
free radical
scavenger and
corrosion protection
in gramma-irradiated
epoxy composites
Jianping He Carbon 2016 Synthesis of a novel functionalised graphene oxide/epoxide
nanocomposite.
ESR analysis on 0.25 wt % functionalised graphene/epoxy
composite after γ-radiation indicates that the graphene
behaves as a free radical scavenger.
Increase in the oxidative stability of the composite due to the
reduction of irradiation ageing speed.
Additional improvements in anti-corrosion effects
Advanced
Coatings;
Radiation
Tolerance
Yes
#96 Monash University,
Australia
Reinforcing Effect of
Graphene Oxide on
Portland Cement
Paste
Wen Hui Duan Journal of
Materials in Civil
Engineering
Patents also filed.
2015 Investigating the reinforcing effects of graphene oxide on
Portland cement paste.
Addition of 0.03 wt % GO into the cement can increase the
compressive strength and tensile strength of the cement by
more than 40 %.
Moreover, GO sheets enhances the degree of hydration of
the cement.
Note: no reports on the effect of radioactive nuclei storage or
radiation effects on graphene-based cements. This could be
interesting area to pursue.
Civil
Engineering/
Construction;
Radiation
Tolerance
Potentially
Page 73
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
Hydrogen Isotope Separation
#97 The University of
Manchester
Sieving hydrogen
isotopes through
two-dimensional
crystals
Andre Geim Science 2016 Demonstrated that monolayers of graphene and boron nitride
can be used to separate hydrogen ion isotopes.
Deuterons permeate through the monolayer crystals much
slower than protons, resulting in a separation factor of ca. 10
at room temperature.
This is ongoing work.
Radionuclide
Remediation
Yes
Graphene-based Electronics
#98 Columbia University
Brookhaven National laboratory
Improving the
radiation hardness of
graphene field effect
transistors (GFETs)
Ioannis
Kymissis
Applied Physics Letters
2016 Investigation into the effects of γ-radiation on graphene-
GFETs.
Devised a method to protect GFETs i.e. radiation-hardened
devices which exhibit minimal performance degradation and
improved stability.
Sensors;
Radiation
Tolerance
Yes
#99 Pennsylvania State
University & Purdue
University
GFETs on undoped
semiconductor
substrates for
radiation detection
Michael Foxe IEEE
Transactions on
Nanotechnology
2012 Simulations of the interaction of γ-radiation on GFETs.
Overall, the paper shows several advantages of using
graphene FETs compared to traditional Si based FETs.
The group from Purdue have published at least another 2
papers on the subject including using GFETs as a neutron
sensor.
Sensors;
Radiation
Tolerance
Yes
Related Research Programs Ongoing at the University of Manchester
Page 74
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#100 The University of
Manchester
EPSRC Funded
Project: “Radiation
Damage in Inorganic
2D Materials”
Prof. Cinzia
Casiraghi & Dr.
Aliaksandr
Baidak
EPSRC Project Ongoing This project will be focused on the synthesis and post-
irradiation characterisation of a number of 2D transition metal
dichalcogenides (TMDCs) and hexagonal boron nitride (h-
BN) in order to elucidate the radiation damage mechanisms
in these materials.
It is expected that the radiation damage in inorganic 2D
materials will be quite different from graphene due to more
complex layered structure and multi-element chemical
composition of these compounds.
The Co60 irradiator and the 5MV tandem ion accelerator at
the Dalton Cumbrian Facility (DCF) will be deployed to
produce lattice damaged specimen by gamma rays and by
heavy ion bombardment, respectively. Radiolytic changes in
inorganic 2D materials will be examined using Raman
Spectroscopy, Fourier Transform Infrared Spectroscopy,
Atomic Force Microscopy, Scanning Electron Microscopy and
Transmission Electron Microscopy. Proposed extensive
characterisation of irradiated two-dimensional materials will
allow to quantify the extent of lattice damage and to gain a
better understanding of the mechanisms of radiation-induced
degradation. The proposed studies will make an important
contribution to the fundamental understanding of radiation
hardness (or instability) of the inorganic 2D materials.
Sensors;
Radiation
Tolerance
Yes
(although
the
research
focus is on
non-
graphene
2D
materials)
Page 75
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#101 The University of
Manchester
EPSRC applied for
funding: “Gamma
Radiolysis as a Tool
for Covalent
Functionalisation of
Graphene”
Prof. Cinzia
Casiraghi & Dr.
Aliaksandr
Baidak
EPSRC Bid Bid
pending
This proposal involves the synthesis of novel functionalised
graphene-based materials by gamma-radiolytic modification
of exfoliated graphene in various organic solvents. We
suggest that gamma radiolysis in liquid media can be used as
a highly efficient and simple synthetic tool to accomplish
covalent functionalisation of graphene. The proposed
radiolytic approach offers the following advantages: (1) the
covalent modification will be performed directly in solutions on
liquid-phase exfoliated graphene sheets, i. e. in a scalable
process suitable for mass production; (2) there is a wide
selection of organic solvents with surface energies matching
that of graphene, making them deployable for liquid-phase
exfoliation technique; (3) each organic solvent has a
characteristic radiolysis mechanism, i.e. there is a wide
choice of various radical species available for radiolytic
functionalisation of graphene; (4) since the exfoliated
graphene is transferred to solution at relatively low
concentrations (typically at ~ 1 wt%), most of the
electromagnetic radiation of a gamma-ray will be absorbed by
a solvent; therefore, we expect that the radiation damage to
the exfoliated graphene to be negligible, whereas radical
production due to radiolytic decomposition of a solvent will be
the dominant process; (5) during gamma radiolysis radicals
are produced uniformly in solution and the rate of the radical
formation can be easily altered by modifying the dose rate of
a radiation source.
Advanced
Materials
Potentially
Page 76
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#102 The University of
Manchester
Unfunded project
“Graphene and 2D
remote sensors for
pools or waste
storage”
Prof. Cinzia
Casriaghi and
Prof. Kostya
Novoselov
N/A N/A Graphene and 2D remote sensors for pools or waste storage.
No more details as of yet.
Sensors Yes
#103 The University of
Manchester
Unfunded project
“Super-hydrophobic
coatings”
Prof. Cinzia
Casriaghi and
IEEE team
N/A N/A Super-hydrophobic coatings.
No more details as of yet.
Advanced
Coatings
Potentially
#104 The University of
Manchester
Radiolytic
Modification of
Graphene Oxide
Nanoflakes for
Selective Extraction
of Radionuclides
Prof. Simon
Pimblott & Dr.
Aliaksandr
Baidak
NDA Bursary
Scholarship
Bid
pending
Overall aim of this project is to develop and to test graphene
oxide based nanomaterials exhibiting high selectivity and
efficiency in removal of radioactive technetium from water.
Our hypothesis is that this goal can be achieved by deploying
a radiolytic approach to enable the fine-tuned modification of
graphene oxide matrix.
The proposed project will pursue the following objectives:
(1) To test feasibility of radiolytic modification of the graphene
oxide to produce derivatives with fine-tuned selectivity of
removal of technetium-99 from water;
(2) To determine which of the radiolytically modified products
exhibit the highest adsorption capacity for the pertechnetate
by performing batch studies with the perchlorate and the
pertechnate anions to mimic Tc-99 extraction;
(3) To establish the preparation protocol producing the lead
nanomaterial for Tc-99 extraction and understand the
mechanisms responsible for its high performance.
Radionuclide
Remediation
Yes
Industry Funded Projects Relating to “Graphene” from Innovate UK/TSB: Duration 2015-2017
Page 77
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#105 KW Special
Projects Limited,
Nquiringminds Ltd.,
Cedar Metals Ltd.,
Carr’s Welding
Technologies Ltd.,
Tiscs Ltd., Brunel
University London,
Innovative
Technology and
Science Ltd.,
Cambridge
Nanomaterials
Technology Ltd.
Power ultrasound as
a generic tool for
micro/nanoscale
processing of
materials
(Competition Title:
Materials and
Manufacturing over
12 months or over
£100k)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2016/20
17
The project goal is a novel generic technology (UltraMAT) for
materials processing of fluid and semi fluid phases that are
widespread in manufacturing e.g. in the welding and
adhesive joining of components, the manufacture of bulk
composite components and in traditional, PM (HIP) and semi
solid casting. The key purpose of UltraMAT is to enable
production of manufactured components with step
improvements in specific strength (yield/ fatigue/ impact) and
modulus, fatigue life and thus lightweighting; driven by
economic and environmental needs to reduce energy
consumption and emissions in manufacture and transport.
The enabling tool is power ultrasound with purpose shaped
force fields for controlled movement and size creation of
uniform nano structures to enable: (1) Production of
homogeneously distributed and shaped nanoscale
particulates, fibres or grains). (2) Enhancement of interlayer
and filler-matrix adhesion bonds. UltraMAT will be validated
through the fabrication and testing of samples of a number of
key structure/joint types of growing importance especially in
aerospace or automotive bodies/engines: (i) Ti/Al fibre
laminates (ii) Ti/Al metal matrix composites with fibre/
particulate (ceramic TiC/SiC), Ti/Al laser welding and (iv) Al
semi solid casting. Homogenisation performance will be
studied using graphene (G) and carbon nanotubes (CNT)
because the strong agglomeration tendencies of G and NT is
impeding their ability to realise commercially, components of
ultra-high specific strength. In short pulse echo mode,
UltraMAT will self-evaluate its performance on line aided by
predictive big analytics.
Advanced
Materials;
Advanced
Manufacture/
Fabrication
Potentially
Page 78
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#106 DZP Technologies
Ltd., L.V.H Coatings
Ltd, University of
Warwick
Scalable
electrophoretic
manufacture of high
density 2-
dimensional
materials for energy
storage applications
(Competition Title:
Manufacturing over
12 months or over
£100k)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2016/20
17
This is a collaborative project between two industrial partners,
DZP Technologies Ltd and LVH Coatings Ltd, and one
academic partner, the University of Warwick. The project will
investigate the feasibility of using electrophoretic deposition to
manufacture electrochemical energy storage of improved
performance and new form factors. Additionally, our
technology will make use of new, graphene-related materials
which have the potential to produce a transformational step
change in the performance of electro-chemical power
devices. In this way, the project is involved with innovation in
both manufacturing technology, and materials development.
The new and improved power devices enabled by our
technology can be used across different power sectors,
including the national grid, distributed power networks and
low-carbon vehicles, in addition to the constantly evolving
consumer electronics sector. Further to energy storage
applications, EPD manufacturing itself can produce novel 2D
material coatings with anti-corrosion and self-lubricating
properties for the automotive, aerospace, and advanced
surface engineering sectors.
Energy/
Energy
Storage;
Advanced
Coating
Potentially
Page 79
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#107 Centre for Process
Innovation Ltd.,
Haydale Ltd.
Smart Filter
Membrane
(Competition Title:
Creating Smart
Products from Smart
Materials)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
Membrane filters can be applied for a variety of industrial
liquid and gas separations applications such as water
desalination, water/oil separation during oil drilling and
industrial waste water treatment. A major operational issue
with filter membranes is their tendency to foul with use over
time, which results in lowering through put, increasing energy
consumption and the need for costly maintenance. The aim
of this project is to develop a low-cost self-cleaning coating
technology based on functionalised graphene, which once
applied to industrial membranes makes them resistant to
fouling. The technology has already been demonstrated
successfully in lab-scale tests. Led by G2O Water Limited,
this project will translate the lab-scale work into a working
robust, reliable manufacturing process which can be scaled-
up to enhance the performance of existing filter membranes.
The coating will be formulated and validated by the
consortium for deployment in a number of different
applications, in order to ensure the resulting smart product
can be taken to market and be readily applied to improve the
performance of a broad range of industrial processes.
The system is currently being transferred for applications in
aqueous systems with desalination applications, with the
ability to trap radionuclides onto membranes selectively. As
the radionuclides are trapped onto the membrane, the filter
can be used for longer.
Membrane;
Advanced
Coatings;
Water
Treatment
Yes
Page 80
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#108 Cranfield University,
Exergy Ltd., Solaris
Photonics Ltd.,
Applied Materials
Technology Ltd.
Low Cost Copper
Transparent
Electrode Material
(LOCUST)
(Competition Title:
Energy Catalyst Rnd
2.)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
Transparent conductive electrode (TCE) is an essential
component for solar cells and other devices such as displays,
currently indium tin oxide (ITO) and silver are the prevailing
choices. ITO and silver are however expensive. ITO has
limited supply, and tends to degrade in performance under
stress, so ITO-replacement TCEs have attracted extensive
interests in the past years. Promising possible replacements
include less expensive transparent conductive oxides, carbon
nanotubes (CNT) or graphene-based thin films, conductive
polymers, and metal grids based TCEs. This consortium aims
to develop low cost and superior, sustainable Cu nanowires
based TCE for solar cells, and explore its application to other
devices.
Advanced
Materials;
Advanced
Coatings
Potentially
Page 81
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#109 Precision Varionic
Internation Ltd.,
Dycotec Materials
Ltd., University
College London
Endurance -
Graphene-based
coatings for durable
wear resistant low
cost position sensors
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
In recent years there has been an exponential increase in
embedded electronics within cars as OEMs strive to satisfy
consumer demand for greater comfort, safety, convenience,
reliability, fuel efficiency, infotainment and fun, and stringent
legislative targets for automotive emissions. Position sensors
represent a key enabling technology used for monitoring and
control of systems throughout the car, from engine
management through to pedal position monitoring.
Consumers demand intelligence as standard and at no extra
cost. The state of the art provides two sensor types: i) contact
based devices (low performance at low cost); and ii) non-
contact devices (high performance at high cost). Utilising the
unique properties of graphene-based coatings (wear
resistance combined with customised conductivity and
barrier) the ENDURANCE consortium will assess the
feasibility for development of a low cost high performance
linear and encoder position sensors enabling realisation of
disruptive solutions meeting well defined user needs. The
ENDURANCE technology has the potential to extend far
beyond the automotive market (£770m) to secondary
markets worth >£7.4 billion.
Sensors;
Advanced
Electronics;
Advanced
Coatings
Potentially
Page 82
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#110 Thomas Swan &
Co. Ltd., Plessey
Semiconductors
Ltd., Nano Products
Ltd., University of
Strathclyde,
Nottingham Trent
University
FlexiLEDs with
printed graphene-
based thermal
management
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
A new UK based mass manufacturing technology will create
flexible plastic sheets with embedded electronics and
microscopic light emitting devices. High compressed
graphene flakes connected to the devices will allow heat to
be drawn away from the devices so they carry on working
efficiently. Formed into many shapes and sizes the devices
could be placed anywhere. They could form part of the
exterior of cars and vans to provide advertising or indicator
and brakes lights. On the inside they could provide efficient
video displays for passenger. In the home the devices could
be built into the walls, ceilings and floors to allow endless
opportunities for lighting the home. By using graphene to
remove the heat these devices will use less energy and last
for longer.
Advanced
Electronics;
Heat Transfer
Potentially
#111 Applied Graphene
Materials Ltd., TWI
Ltd., Sherwin-
Williams Protective
& Marine Coatings
GRAphene
protective Coatings –
GRACe
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
Each year, it is estimated that corrosion costs the economy
£10 billion per annum in the repair, maintenance and
replacement of structures in Britain. Organic coatings loaded
with hazardous or environmentally unfriendly metals such as
zinc and chromates are commonly used to protect such
structures and so it is desirable to find improved green
alternative solutions. Graphene has been identified as a
suitable green anti-corrosive additive and Project GRACe will
investigate and develop the potential of graphene-based anti-
corrosive coatings. In addition, graphene has been identified
with the ability to mitigate risks of fires, so GRACe will also
explore the potential for using graphene in fire retardant,
protective coatings.
Advanced
Coatings;
Corrosion
Yes
Page 83
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#112 Marshall of
Cambridge
Aerospace Ltd.,
University of
Sheffield, Emyrus
Ltd., Netcomposites
Ltd.
Inkjet Printing of
Plasma
Functionalised
Graphene to Deliver
Multifunctional
Polymer Composites
for Aerospace
Applications
(PlasmaGraph)
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
The objective of the PlasmaGraph project is to develop a
method by which plasma functionalised graphene can be
selectively deposited onto fibre reinforced composites to
deliver multi-functionality to aerospace structures. There are
three main elements to deliver to meet this overall objective:-
Plasma functionalised graphene; to prevent the re-
agglomeration of the graphene in a dispersion and the re-
agglomeration of the graphene can both reduce the inherent
properties of the graphene and, for inkjet printing, prevents
use of graphene dispersions as the re-agglomerated material
can block print heads;- Inkjet printing of graphene dispersions
onto fabric preforms; this allows the selective placement of
graphene into structural composites and will deliver
multifunctional benefits;- Manufacturing of graphene
functionalised composite components; this requires the inkjet-
printed graphene to remain in-situ when the final composite
part is manufactured so that the benefits are retained, but
also so that there is no release of the graphene to the
environment during processing.
Advanced
Coatings
Potentially
Page 84
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#113 NPL Management
Ltd., Oxford
Instruments
Nanotechnology
Tools Ltd.,
University of
Manchester
Industrial feasibility
test of a graphene-
enabled turnkey
quantum resistance
system
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
Graphene enabled Quantum resistance system will provide
the high-end electronics instrumentation industry with a
primary resistance standard which can be used directly on
the factory floor dramatically reducing the calibration
traceability chain and improving the precision of electronic
instrumentation. The quantum Hall effect (QHE) is one of the
most fundamental phenomena in solid-state physics. Its
observation in graphene was the litmus test that proved that
this material is a true 2-dimensional crystal of the highest
quality. The QHE is also the cornerstone of electrical
metrology as it is the primary realisation of the unit for
resistance, the ohm. The proposed turnkey system will be
cryogen free and operating at low magnetic fields. It will
enable resistance calibration with unprecedented accuracy to
industrial companies and reduce the cost and time from
design to product.
Advanced
Electronics
Potentially
#114 Meggit Aerospace
Ltd. Haydale
Composite
Solutions Ltd.
The effect of
graphene additions
on carbon-carbon
composite materials
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
Project Creosote investigates the potential of graphene
additives to Carbon/Carboncomposites in a range of thermal
management applications.
Advanced
Materials; Heat
Transfer
Potentially
Page 85
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#115 Haydale Composite
Solutions Ltd.,
University of
Warwick
INdustrial
PRocessing Of Nano
Epoxies (INPRONE)
(Competition Title: Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
The aim of this interesting project is to prove the feasibility of
upscaling the manufacture (using industrially relevant
processes) of Graphene enhanced epoxy masterbatch. In
doing so we will prove that we can impart radical
improvements in thermal properties of epoxy resins that have
previously only been shown at academic and lab scale level.
Additional improvements may also be seen such as material
durability, resistance to wear and improvements in thermal
cycling.
Advanced
Materials
Potentially
#116 University of
Bradford, Thomas
Swan & Co. Ltd,
DelStar
International Ltd.,
Haydale Ltd.
GraNet - Graphene /
Polypropylene
Composite Nets for
Filtration
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
This project uses graphene to produce composites with
polyolefins to give a step change in performance for
lightweight extruded oriented products used in specialist
applications. The project team will; gain an understanding of
how graphene can enhance the performance of polymer
composites, especially in relation to physical strength and
operating temperature develop techniques to achieve
dispersion of graphene into a polymer matrix at production
scale without damaging the platelet structure and reducing
the benefits of addition. understand what impact graphene
has on polymer processability and rheological properties,
including trial sat production scale (processing up to 2.5kg of
graphene to produce 250kg of composite) model the impact
that addition of graphene has on product cost at predicted
volumes. develop a value proposition for prototype products
and gain feedback from customers in the target markets
Advanced
Materials
Yes
Page 86
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#117 University of
Cambridge, Tata
Steel UK Ltd.
Graphene coatings
on steel for large
scale energy storage
applications
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
From burning firewood to oil, the ability to store energy and
use it at our command has been responsible for the biggest
transformations of humanity in the course of history. Today,
electrochemical devices, namely batteries and
supercapacitors which are predominantly used for portable
energy, are probably the biggest limitation to the fast
development of portable electrical appliances from mobile
phones to cars, and significant improvements in these
technologies are urgently required. This project aims to
combine graphene with steel as a charge collecting material
in batteries and other advanced energy storage devices.
Graphene is a good conductor as well as a good barrier
providing electrochemical stability of the steel. Success on
this project would allow improvements in performance as well
as significant cost reduction in batteries and supercapacitors
alike.
Energy/Energy
Storage;
Potentially
#118 Haydale Ltd.,
University of Bath
Multi-functional skins
incorporating carbon
(MuSIC)
(Competition Title:
Advancing the
commercial
applications of
graphene)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
The aim of the project is to assess the feasibility of employing
graphene-based polymer skins for sensing and deicing
applications. There are major issues associated with deicing
are in aircraft, at airports, transmission power lines,
instrumentation, antenna masks, wind turbines and the
exploration of cold environments (e.g. oil and gas). Such a
sensing surface can be integrated with thermally active
(shape changing) structures to achieve structural deflection
for combined thermal-mechanical de-icing. The opportunity to
limit the extent of ice build-up on structures has broad
application opportunities and enable light weight structures
with reduced material costs and fuel saving for mobile
applications and improved performance for instrumentation.
Advanced
Coatings;
Sensors
Potentially
Page 87
# Institution/
Research Group/
Organisation
Title Author/Lead
Researcher
Source Year Research/ Project Summary Research
Area
Relevant?
#119 NPL Management
Ltd., DZP
Technologies Ltd.
Two-Dimensional
graphene-related
TRansition metal
dichalcogenides for
ultracapacitor
ENergy storage
Devices (2D
TREND)
(Competition Title:
Energy Catalyst R3)
N/A Innovate
UK/TSB:
Duration 2015-
2017
2015/20
16
The discovery of graphene inspired exciting new research in
to other two-dimensional (2D) materials, most notably the 2D
transition metal dichalcogenides (TMDs) which similarly to
graphene can be exfoliated into atomically thin nano-sheets
with unusual electronic and optical properties. To date, most
research on TMDs has remained in the laboratory, in contrast
to graphene which is already applied in new commercial
products. This project, entitled Two-Dimensional TRansition
metal dichalcogenides for ultra-capacitor ENergy storage
Devices(2D TREND), aims to establish the feasibility of 2D-
TMD materials for scale up and use in ultra-capacitor energy
storage for the smart grid. The project will develop methods to
exfoliate 2D-TMD materials to nano-sheets and integrate
them into supercapacitor electrodes. This will be
complemented by advanced structural and chemical
characterisation to develop understanding of the material
properties. The project will demonstrate electrochemical cells
which will enable the evaluation of the 2D-TMD materials for
real-life energy storage.
Energy/
Energy
Storage
Potentially
Page 88
Appendix B The NDA Estate’s Research and Development Needs Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
Spent Fuels – defines NDA approach to managing the diverse range of spent nuclear fuels for which we are responsible
Spent Magnox Fuel
• Improved characterisation technologies that would provide Sellafield Ltd with a better understanding of the condition of the reprocessing facility could be required;
• Development of technologies to treat the small amounts of fuels left over once Magnox reprocessing operations cease;
• Further technologies to dry store and/or immobilise legacy Magnox fuels to manage materials held within Legacy Ponds and Silos (LP&S) at Sellafield.
N/A
Spent Oxide Fuel
• Improved characterisation technologies that would provide Sellafield Ltd with a better understanding of the condition of the reprocessing facility could be required;
• Pond storage of spent oxide fuel is planned for a significant period. Therefore technologies that improve NDAs existing approach to treating pond water are of interest:
o Technologies that monitor spent oxide fuel and associated pond furniture under wet storage conditions will be required;
o In situ technologies that monitor the precursors of spent oxide fuel corrosion are of particular interest;
• In the longer term technologies associated with drying, storage and disposal of spent oxide fuel are of interest to NDA.
N/A
Page 89
Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
Spent Exotic Fuel
• Improved technical options for long-term storage of specific exotic fuels;
• Improving NDAs understanding of potential long-term behaviours of additive materials and exotic fuel claddings under wet or dry storage conditions;
• Identifying functional requirements and treatment technologies to facilitate storage and final disposition (e.g. disposal) of exotic fuels;
• Technologies associated with monitoring, storage, treatment and disposal of spent exotic fuels are therefore of interest.
• Not relevant to new material/technology development
Nuclear Materials – defines NDA approach to dealing with the inventory of uranics and plutonium currently stored on some of our sites
Plutonium
• Technologies for monitoring waste packages and stores that improve upon existing approaches are therefore of interest;
• Development work to underpin the treatment process operating conditions for the full range of materials that must be treated;
• Research into technologies to extend the amount of plutonium that is suitable for reuse.
• Not relevant to new material development
Uranics • Technologies that would make NDAs uranics inventory more
saleable. • Not relevant to new
material/ development
Integrated Waste
Management – considers how NDA manage all forms of waste arising from operating and
Radioactive Waste
Reprocessing
• Understanding, maintaining and extending the lifetime of existing infrastructure is ongoing;
• There is however a need to understand how the existing facilities will treat wastes from POCO of the reprocessing facilities and how existing treatment facilities could be modified to manage new wastes.
• Not relevant to new material/technology development
Page 90
Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
decommissioning NDA sites, including waste retrieved from legacy facilities
Some of the key areas of research include:
o Understanding the benefits of co-processing reprocessing wastes with POCO wastes;
o Understanding the impact of solids (formation, transport and treatment) on POCO of HAL treatment process;
o Wasteform development (e.g. glass formulation) for vitrification of POCO HAL feeds;
o Options for treating effluents that allow decommissioning of existing facilities (e.g. SETP) to take place.
• There are also synergies with the interim storage of other packaged wastes (e.g. decommissioning waste). Some of the key areas of research include:
o Remote monitoring of waste packages (e.g. corrosion);
o Remote monitoring of stores (e.g. humidity);
• Research into the disposal of HAW is on-going and being led by RWM [2]. Key areas of research include:
o Role and evolution of barriers (package evolution; engineered barrier system; geosphere);
o Release and movement of contaminants through the multi-barrier system (radionuclide behaviour; gas generation and migration; biosphere);
o Control of low probability events and their outcome (criticality
• Not relevant to new material/technology development
• Not relevant to new material/technology development
2 Radioactive Waste Management. Geological Disposal – Science and Technology Plan (NDA/RWM/121). 2016
Page 91
Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
safety; waste package accident performance);
• RWM also has projects investigating specific technical topics:
o Disposal of wastes containing carbon-14;
o Disposal of high-heat-generating wastes;
o Disposal of uranium (depleted, natural and low enriched);
o Maintaining and developing the range of geological disposal concepts;
These disposal R&D requirements are common across radioactive wastes from reprocessing, legacy facilities and operational and decommissioning wastes.
Legacy Facilities
• For approaches that involve containerisation of waste, there may be opportunities to optimise future treatment of these packages through better understanding of the evolution of the waste and waste package or the development of new treatment technologies (e.g. thermal);
• Some of the key areas of research include:
o Reduced cost waste packages;
o Remote monitoring of waste packages (e.g. corrosion, hydrogen evolution);
o Remote monitoring of stores (e.g. humidity, temperature).
• Not relevant to new material/technology development
Operational and Decommissioning Wastes
• Some of the key areas of research include:
Page 92
Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
o Improved encapsulants (e.g. reduced cost, higher waste incorporation, increased security of supply, easier processability, increased compatibility with wastes);
o Improved treatment technologies (e.g. thermal).
• Not relevant to new material development
Liquid and Gaseous
Discharges
• The liquid and gaseous discharges for decommissioning activities are more varied. Particularly at Sellafield, the variety can be challenging from a scheduling and compatibility viewpoint. Key areas of research include:
o Modular and mobile effluent treatment facilities to allow the decommissioning of existing effluent facilities or to manage short-term effluent requirements;
o In-line monitoring technologies to avoid the transport of samples and increase sampling interval.
N/A
Non-Radioactive Waste
The ‘Operational and Decommissioning Wastes’ section of the NDA Technical Baseline document [2] covers both radioactive and non-radioactive wastes generated by both the operation and decommissioning of NDA facilities. Therefore any non-radioactive waste R&D needs will have been highlighted within this section above.
• Repetition of other requirements within other Strategic Topics
Site
Decommissioning
& Remediation – defines NDA approach to decommissioning redundant facilities and managing land quality in order that
Decommissioning
Whilst the approach to Site Decommissioning is often facility specific there are however some common technical challenges:
• Improved data visualisation tools to assist decision making;
• In situ characterisation to determine level of contamination:
o Portable versions of existing characterisation techniques;
o Non-destructive evaluation technologies;
• Not relevant to new material development
Page 93
Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
each site can be released for its next planned use
• Improved decontamination techniques:
o Increased efficiency and effectiveness;
o Reduction in secondary waste;
o Removal of heels and residues from process vessels;
• Remote or enhanced operation for extreme conditions (e.g. high dose, confined spaces):
o Enhanced tools and techniques for air-fed suit decommissioning operations;
o Enhanced tele-operation (e.g. virtual reality and haptics);
o Robotics and autonomous systems;
• Technologies and approaches for monitoring facilities and their contents over extended periods of C&M/deferral;
• Waste treatment technologies for decommissioning wastes:
o Sort and segregation approaches; Similarly whilst the approach to Site Remediation is often site specific, there are however some common technical challenges:
• Improved groundwater monitoring:
o Increased automation to increase frequency of monitoring and reduce cost;
o Increased information (e.g. isotopic ratios, chemical speciation, improved limit of detection) to identify source of contamination;
• Not relevant to new material development
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Strategic Theme Strategic Topic Research and Development Need Explanation for Rejecting
R&D Need
o Increased information (e.g. in situ groundwater flux measurement) to improve predictions of movement of contaminants;
o Improved statistical approach to monitoring programme;
• Improved data visualisation tools to assist decision making;
• Improved knowledge regarding interactions of radionuclides with the environment:
o Refine or eliminate assumptions in conceptual and predictive models;
• Techniques for early detection of leaks from existing facilities;
• In situ remediation of contaminated ground:
o Techniques (e.g. bioremediation) that either reduce or limit the spread of contaminants and can be applied on sites with facilities still present;
• Ex situ remediation of contaminated ground:
o Techniques (e.g. sort and segregation; thermal treatment) that reduce the volume of contaminated ground that requires further long-term management.
• Not relevant to new material/technology development
• Not relevant to new material/technology development